Polyrotaxane, Production Method Therefor, and Optical Composition Containing said Polyrotaxane

ABSTRACT

The present invention provides an optical composition from which an optical article having reduced poor appearance such as cloudiness and optical strain during lens base material production can be obtained, and when a photochromic compound is added, a photochromic cured body having excellent photochromism and mechanical strength can also be formed, and a polyrotaxane used therefor. The polyrotaxane has a composite molecular structure formed of an axle molecule and a plurality of cyclic molecules clathrating the axle molecule, satisfying at least one of (X) and (Y). (X): A side chain having a secondary or tertiary hydroxyl group is introduced into at least part of the cyclic molecule of the polyrotaxane. (Y): A side chain having a group represented by -A (A is an organic group, and contains at least one hydroxyl group) is introduced into at least part of the cyclic molecule of the polyrotaxane, and a pKa of the hydroxyl group of the compound represented by H-A is 6 or more and less than 14.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/757,062, filed, Mar. 2, 2018, which is the U.S. national phase ofInternational Application No. PCT/JP2016/075463 filed Aug. 31, 2016, andclaims priority to Japanese Patent Application Nos. 2015-174232 and2015-175101, filed Sep. 3, 2015 and Sep. 4, 2015, respectively, thedisclosures of all of which are hereby incorporated in their entirety byreference.

TECHNICAL FIELD

The present invention relates to a new polyrotaxane and a productionmethod therefor, and an optical composition containing the polyrotaxane.

BACKGROUND ART

A polyrotaxane has a specific structure of having a cyclic molecule, anda straight-chain molecule threaded through the cyclic molecule in askewered manner, and blocking groups arranged at both ends of thestraight-chain molecule to prevent the cyclic molecule from beingseparated from the straight-chain molecule. In this polyrotaxane, thecyclic molecule can move on the straight-chain molecule relatively.Therefore, the polyrotaxane has various characteristics, particularly,excellent mechanical characteristics, and is expected to be applied anddeveloped in various manners, and has also been used in an opticalmaterial such as a contact lens (see Patent literature 1), or the like.Meanwhile, in many optical materials, plastic lenses are used, andlighter in weight, harder to break and dyeable in comparison withinorganic lenses, and therefore have been widely used rapidly in everyindustrial field in recent years. One of the fields is a field of aneyeglass lens. The eyeglass lens is required to satisfy many functionssuch as transparency, excellent durability, easy dyeability, and resinstrength enough to withstand processing, and various resin materials forlenses have been developed and used so far. Moreover, one of kinds ofthe eyeglass lenses is a photochromic eyeglass lens. The photochromiceyeglass lens means a material which is immediately colored in anoutdoor place where the material is irradiated with light includingultraviolet rays such as sunlight to function as sunglasses, and in anindoor place where the material is not irradiated with such light, thematerial is faded to function as ordinary transparent eyeglasses. Ademand therefor has increasingly grown in recent years.

In order to provide the optical material with photochromism, aphotochromic compound is generally used in combination with a plasticmaterial. Specifically, the following means are known: (a) a method fordissolving a photochromic compound into a polymerizable monomer, andpolymerizing the resulting mixture to directly shape an optical materialsuch as a lens, which method is called a kneading method; (b) a methodfor providing, on a surface of a plastic molded product such as a lens,a resin layer into which a photochromic compound is dispersed, bycoating or cast polymerization, which method is called a laminationmethod; and (c) a method for bonding two optical sheets with an adhesivelayer formed by an adhesive material resin into which a photochromiccompound is dispersed, which method is called a binder method.

Incidentally, the optical material such as an optical article providedwith the photochromism is further required to satisfy thecharacteristics as described below.

(I) A degree of coloring (initial coloring) in a visible light regionbefore being irradiated with ultraviolet rays should be low.

(II) A degree of coloring (color optical density) upon being irradiatedwith ultraviolet rays should be high.

(III) A rate (color fading rate) from stopping irradiation withultraviolet rays to return to an original state should be high.

(IV) Durability against repetitive reversible action of colordevelopment and color fading should be satisfactory.

(V) Storage stability should be high.

(VI) The optical material should be easily shaped into various shapes.

(VII) Photochromism should be provided without causing reduction ofmechanical strength.

Accordingly, also upon producing the optical material havingphotochromism or the like by using the means (a) to (c) described above,various proposals have been made so that the requirements as describedabove may be satisfied. With regard to the color optical density, thecolor fading rate or the like, however, development of superbphotochromism has been required in a current status.

For example, the kneading method described above has an advantage ofcapability of producing a photochromic plastic lens in bulk and at a lowcost by using a glass mold, in which most of the photochromic plasticlenses are currently produced using this method.

In the kneading method, however, sufficient strength is required for alens base material. Therefore, it is necessary to enhance mechanicalstrength of a matrix resin in which the photochromic compound isdispersed. Therefore, it becomes difficult to develop excellentphotochromism. More specifically, a degree of freedom of molecules inthe photochromic compound existing in the matrix resin is reduced, andtherefore a photochromic reversible reaction is adversely affected.

With regard to such a kneading method, for example, Patent literature 2describes a technique on adding a photochromic compound to a monomercomposition containing an isocyanate monomer and a thiol monomer.Moreover, Patent literature 3 discloses a photochromic curablecomposition containing a specific (meth)acrylic polymerizable monomerand a photochromic compound.

Photochromic lenses shaped by allowing polymerization curing of thesecompositions, however, are unsatisfactory in view of photochromiccharacteristics, while the mechanical strength is high.

On the other hand, in the lamination method or the binder method, thephotochromism is developed in a thinner layer formed on surfaces ofvarious base materials in comparison with the kneading method describedabove. Therefore, in order to develop the color optical densityequivalent to the density according to the kneading method, thephotochromic compound is required to be dissolved thereinto with a highconcentration. In the above case, such problems have remained asinsufficiency of solubility and occurrence of precipitation duringstorage depending on a kind of the photochromic compound. Moreover, thelayer in which the photochromism is developed is thin, and thereforedurability of the photochromic compound has been deteriorated in severalcases.

For example, Patent literature 4 discloses a method for coating aphotochromic curable composition on a plastic lens by spin coating orthe like to allow photocuring of the resulting material to form aphotochromic coating layer (This lamination method is also called acoating method.).

Moreover, Patent literature 5 discloses a method for forming aphotochromic layer by securing a space between a plastic lens and aglass mold by using a member such as an elastomer gasket, apressure-sensitive adhesive tape or a spacer, and flowing a photochromiccurable composition into the space to allow polymerization curingthereof (hereinafter, also called two-step polymerization method).

Further, Patent literature 6 discloses a production method for alaminated sheet prepared by bonding a transparent carbonate sheettherewith by a polyurethane resin adhesive layer containing aphotochromic compound (binder method).

Also in all the methods in Patent literature 4 to 6, however, thephotochromism is developed in the thin layer in which the photochromiccompound is blended. Therefore, when the photochromic compound havinglow solubility is used, the color optical density tends to be reduced,and further the durability of the photochromic compound has been alsodeteriorated in several cases.

Patent literature 7 discloses a lamination method for forming aphotochromic coating layer by coating a photochromic urethane curablecomposition composed of polyol, isocyanate and the like on a plasticlens by spin coating or the like to allow thermal curing thereof. Alsoin this method, however, sufficient color optical density is unable tobe secured.

As an art for solving the problems described above, Patent literature 8discloses a photochromic composition consisting of a polyrotaxane havinga composite molecular structure formed of an axle molecule and aplurality of cyclic molecules clathrating the axle molecule, and havinga side chain containing a hydroxyl group in a part of the cyclicmolecule, a polyisocyanate monomer and a photochromic compound. In thephotochromic composition, both high mechanical strength caused by aurethane bond by incorporating the polyrotaxane thereinto, and excellentphotochromism (color optical density and a color fading rate) byexistence of a free space formed by bonding of the polyrotaxane to apart of the polyurethane are satisfied (see Patent literature 8).

PATENT LITERATURE

Patent literature 1: WO 2005/095493 A

Patent literature 2: WO 2012/176439 A

Patent literature 3: WO 2009/075388 A

Patent literature 4: WO 2011/125956 A

Patent literature 5: WO 2003/011967 A

Patent literature 6: WO 2013/099640 A

Patent literature 7: WO 2001/055269 A

Patent literature 8: WO 2015/068798 A

Patent literature 8 above describes evaluation results indicating alevel having substantial no problem on moldability (optical strain andcloudiness). When an evaluation with higher accuracy is conducted,however, the moldability has become insufficient in several cases.Moreover, when various lens shapes have been evaluated in a similarmanner, in particular, a problem of moldability has become significantin the case of a thick lens, and room for further improvement hasremained.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide an opticalcomposition from which an optical article having reduced poor appearancesuch as cloudiness and optical strain during producing a lens basematerial can be obtained, and when a photochromic compound is addedthereto, a photochromic cured body having good photochromism andmechanical strength in addition thereto can be formed, and an object ofthe present invention is also to provide a production method therefor,and a new polyrotaxane used for the optical composition.

The present inventors have diligently continued to conduct study inorder to solve the problems described above. As a result, the presentinventors have found out that, when a polymerizable group reacting withan iso(thio)cyanate group of a polyrotaxane is a primary hydroxyl group,reactivity with the iso(thio)cyanate group is excessively high, andtherefore poor performance is easily caused. Moreover, the presentinventors have found that the poor performance is caused in many cases,when a pKa of a compound having a hydroxyl group corresponding to anorganic group having the hydroxyl group is less than 6 or 14 or more.The present inventors have found out that, when the pKa of the hydroxylgroup reacting with the iso(thio)cyanate group of the polyrotaxane is 14or more, the reactivity with the iso(thio)cyanate group is excessivelyhigh, and therefore the poor performance is easily caused. Morespecifically, the present inventors have obtained findings in which, ifone molecule of the polyrotaxane has a high molecular weight of severalhundred thousands or more, and therefore viscosity of the opticalcomposition becomes high, and the reaction heterogeneously progresses,phase separation with other monomers is easily caused, and poormoldability is easily caused. Moreover, the present inventors haveobtained findings in which, in the case of the hydroxyl group the pKa ofwhich is less than 6, the reactivity with the iso(thio)cyanate isexcessively low, and therefore the hydroxyl group exists in the form ofan unpolymerized monomer, and thus the reaction heterogeneouslyprogresses, and the phase separation and the poor moldability are easilycaused.

More specifically, if the reactivity is excessively high upon obtainingthe optical article such as the plastic lens, a polymerization reactionlocally progresses and a molded body becomes heterogeneous, andtherefore a stria causing the optical strain is conceivably formed.Moreover, when the polymerization is unable to be controlled and a largequantity of polymerization heat that does not follow polymerizationconditions is produced, the stria is conceivably formed also byoccurrence of convection. Further, the present inventors have found thatthe polymerization reaction locally progresses and the molded bodybecomes heterogeneous, and therefore a polyrotaxane-rich oligomer isformed, and the phase separation is caused by such an oligomer, and thuscloudiness is caused.

Accordingly, as one aspect for reducing the reactivity, the presentinventors have succeeded in solving such problems by using a newpolyrotaxane having a secondary or tertiary hydroxyl group in a sidechain introduced into a cyclic molecule to reduce the reactivity of thepolyrotaxane with iso(thio)cyanate, and have completed the presentinvention.

Moreover, as another aspect for reducing the reactivity, the presentinventors have succeeded in solving such problems by using a newpolyrotaxane having a hydroxyl group a pKa of which is 6 or more andless than 14 in a side chain introduced into a cyclic molecule to reducethe reactivity of the polyrotaxane with iso(thio)cyanate, and also tokeep the polyrotaxane reactable with the iso(thio)cyanate, and havecompleted the present invention.

More specifically, the present invention relates to a polyrotaxanehaving a composite molecular structure formed of an axle molecule and aplurality of cyclic molecules clathrating the axle molecule, andsatisfying at least one of requirements (X) and (Y), and also relates toa production method therefor and an optical composition containing thepolyrotaxane:

requirement (X): a side chain having a secondary or tertiary hydroxylgroup is introduced into at least part of the cyclic molecule of thepolyrotaxane; and

requirement (Y): a side chain having a group represented by thefollowing formula (1):

-A   (1)

(where, A is an organic group having 1 to 10 carbon atoms and containsat least one hydroxyl group) is introduced into at least part of thecyclic molecule of the polyrotaxane; and a pKa of a hydroxyl group of acompound represented by the following formula (2):

H-A   (2)

is 6 or more and less than 14.

An optical composition in which a polyrotaxane satisfying at least oneof requirements (X) and (Y) is used as the polyrotaxane to suppressmoldability and cloudiness, as indicated in Examples described later.Thus, an optical article having good moldability and high mechanicalstrength can be produced with a sufficient yield. Further, upon adding aphotochromic compound to the optical composition to produce aphotochromic lens, the photochromic lens also having excellentphotochromism (color optical density and a color fading rate) can beproduced.

In the present invention, the polyrotaxane satisfying the requirement(X) is used to reduce the reactivity with the iso(thio)cyanate incomparison with a primary hydroxyl group. Thus, polymerization can becontrolled and the moldability and the cloudiness described above can besuppressed. Further, the polyrotaxane has the side chain. Thus, acrosslinking structure can be formed, and excellent mechanical strengthcan be obtained as well.

In the present invention, the polyrotaxane satisfying the requirement(Y) is used to suppress the reactivity with the iso(thio)cyanate. Thus,a rate of polymerization can be adjusted and the moldability and thecloudiness described above can be suppressed. Further, the polyrotaxanehas the side chain. Thus, the crosslinking structure can be formed, andtherefore the excellent mechanical strength can be obtained as well.

Further, also upon adding the photochromic compound thereto to produce aphotochromic optical article, excellent photochromic characteristics canbe developed by using the polyrotaxane according to the presentinvention. More specifically, the cyclic molecule of the polyrotaxane isformed to be slidable on the axle molecule. Therefore, a space is formedaround the cyclic molecule. A reversible structural change of thephotochromic compound is immediately caused by this space. As a result,the color fading rate and the color optical density are improved.Further, the reversible structural change of the photochromic compoundexisting in the vicinity of a highly flexible side chain can be furtherimmediately caused by introducing the cyclic molecule in which the sidechain is introduced thereinto.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram showing a molecular structure of apolyrotaxane used in the present invention.

DESCRIPTION OF THE INVENTION

A polyrotaxane according to the present invention has a compositemolecular structure formed of an axle molecule and a plurality of cyclicmolecules clathrating the axle molecule, and satisfies at least one ofrequirements (X) and (Y) ; moreover, an optical composition according tothe present invention contains the polyrotaxane according to the presentinvention:

requirement (X): a side chain having a secondary or tertiary hydroxylgroup is introduced into at least part of the cyclic molecule of thepolyrotaxane; and requirement (Y): a side chain having a grouprepresented by the following formula (1):

-A   (1)

(where, A is an organic group having 1 to 10 carbon atoms and containsat least one hydroxyl group) is introduced into at least part of thecyclic molecule of the polyrotaxane; and a pKa of a hydroxyl group of acompound represented by the following formula (2):

H-A   (2)

is 6 or more and less than 14.

Hereinafter, each component structuring the present invention will bedescribed.

In addition, unless otherwise specified herein, as described above, thepKa of the hydroxyl group refers to the pKa of the hydroxyl group when acompound H-A represented by the formula (2) is formed by substituting,for hydrogen, an atom in a bonding site at which the group representedby the formula (1) in the polyrotaxane according to the presentinvention is bonded with the side chain.

In addition, the polyrotaxane having the composite molecular structureformed of the axle molecule and the plurality of cyclic moleculesclathrating the axle molecule and satisfying the requirement (X) is alsodescribed as the polyrotaxane according to Aspect I; and thepolyrotaxane having the composite molecular structure formed of the axlemolecule and the plurality of cyclic molecules clathrating the axlemolecule and satisfying the requirement (Y) is also described as thepolyrotaxane according to Aspect II. Moreover, the polyrotaxaneaccording to the present invention is also described as the polyrotaxane(A).

As shown in FIG. 1, the polyrotaxane is shown by “1” as a whole. Apolyrotaxane molecule has a composite molecular structure formed of achain axle molecule “2” and a cyclic molecule “3”. More specifically, aplurality of cyclic molecules “3” clathrates the chain axle molecule “2”and the axle molecule “2” threads through an inside of a ring of thecyclic molecule “3”. Accordingly, the cyclic molecule “3” can freelyslide on the axle molecule “2”, but bulky end groups “4” are formed atboth ends of the axle molecule “2”, in which the cyclic molecule “3” isprevented from being dethreaded from the axle molecule “2”.

As described above, such a cyclic molecule “3” of the polyrotaxane isformed to be slidable on the axle molecule “2”. Therefore, when aphotochromic cured body including the photochromic compound is produced,a space is formed around the cyclic molecule, and a reversiblestructural change of the photochromic compound is immediately caused bythis space. As a result, a color fading rate and color optical densityare improved.

<Polyrotaxane in which a Side Chain Having a Secondary or TertiaryHydroxyl Group is Introduced into at least Part of a Cyclic Molecule(Polyrotaxane According to Asptect 1)>

In the polyrotaxane according to Aspect 1, a side chain “5” having asecondary or tertiary hydroxyl group is introduced into at least part ofa cyclic molecule.

Moreover, in the present invention, the polyrotaxane may have a primaryhydroxyl group, in addition to the secondary or tertiary hydroxyl group,in the side chain. From a viewpoint of moldability, however, when thetotal mole number of the primary, secondary, and tertiary hydroxylgroups in the side chain is taken as 100%, a proportion of the primaryhydroxyl group is preferably 50% or less.

In the polyrotaxane according to Aspect 1, such a side chain “5” havingthe secondary or tertiary hydroxyl group is introduced into the ring tofacilitate to react the iso(thio)cyanate compound, while thepolymerization with the iso(thio)cyanate compound or the like iscontrolled, to be described later, and an optical article havingimproved moldability can be obtained. Moreover, a proper space can befurther reliably formed between adjacent axle molecules, a clearance inwhich a reversible reaction of the photochromic compound molecule isallowable can be reliably secured, and excellent photochromism can beconceivably developed. Further, such a side chain “5” causes formationof a crosslinking structure in the polyrotaxane. Thus, mechanicalstrength of the photochromic cured body formed using the opticalcomposition according to the present invention can be improved.

<Polyrotaxane in which a Side Chain Having a Group Represented by theFormula (1), a pKa of a Hydroxyl Group Being 6 or More and Less than 14,is Introduced into at Least Part of an End of the Side Chain of a CyclicMolecule (Polyrotaxane According to Aspect II)>

In the polyrotaxane according to Aspect II, in which a side chain “5”being characterized in that the side chain having the group representedby the formula (1), the pKa of the hydroxyl group being 6 or more andless than 14, is introduced thereinto is introduced into at least partof the cyclic molecule.

Moreover, in the present invention, the polyrotaxane may have thehydroxyl group the pKa of which is less than 6 or 14 or more in the sidechain. From the viewpoint of the moldability, however, when the totalmole number of the hydroxyl groups in the side chain is taken as 100%, aproportion of the hydroxyl group the pKa of which is less than 6 or 14or more is preferably 50% or less.

In the polyrotaxane according to Aspect II, such a side chain “5” havingthe hydroxyl group the pKa of which is 6 or more and less than 14 isintroduced into the ring to facilitate to react the iso(thio)cyanatecompound, while the polymerization with the iso(thio)cyanate compound iscontrolled, to be described later, and the optical article havingimproved moldability can be obtained. Moreover, the proper space can befurther reliably formed between the adjacent axle molecules, theclearance in which the reversible reaction of the photochromic compoundmolecule is allowable can be reliably secured, and the excellentphotochromism can be conceivably developed. Further, such a side chain“5” causes formation of the crosslinking structure in the polyrotaxane.Thus, the mechanical strength of the photochromic cured body formedusing the optical composition according to the present invention can beimproved.

In the polyrotaxane according to the present invention, as the axlemolecule, various materials can be used. For example, a chain portionmay have a straight chain or branched chain, as long as the chainportion can thread through the ring of the cyclic molecule, and isgenerally formed of a polymer.

Specific examples of the polymer that forms such a chain portion of theaxle molecule include: polyvinyl alcohol; polyvinyl pyrrolidone; acellulose-based resin (such as carboxymethyl cellulose, hydroxyethylcellulose and hydroxypropyl cellulose); polyacrylamide; polyethyleneoxide; polyethylene glycol; polypropylene glycol; polyvinyl acetal;polyvinyl methyl ether; polyamine; polyethyleneimine; casein; gelatin;starch; an olefin-based resin (such as polyethylene and polypropylene);polyester; polyvinyl chloride; a styrene-based resin (polystyrene and anacrylonitrile-styrene copolymer resin); an acrylic resin (such aspoly(meth)acrylate, polymethyl methacrylate, polymethyl acrylate and anacrylonitrile-methyl acrylate copolymer resin); polycarbonate;polyurethane; a vinyl chloride-vinyl acetate copolymer resin; polyvinylbutyral; polyisobutylene; polytetrahydrofuran; polyaniline; anacrylonitrile-butadiene-styrene copolymer (ABS resin); polyamide (suchas nylon); polyimide; polydiene (such as polyisoprene andpolybutadiene); polysiloxane (such as polydimethylsiloxane);polysulfone; polyimine; polyacetic anhydride; polyurea; polysulfide;polyphosphazene; polyketone; polyphenylene; and polyhaloolefin. Thesepolymers may be appropriately copolymerized or may be modified.

A preferred material as the polymer that forms the chain portion in thepresent invention include: polyethylene glycol; polyisoprene;polyisobutylene; polybutadiene; polypropylene glycol;polytetrahydrofuran; polydimethylsiloxane; polyethylene; polypropylene;polyvinyl alcohol; or polyvinyl methyl ether, and most preferablypolyethylene glycol.

Further, the bulky groups to be formed at both ends of the chain portionare not particularly limited, as long as the group prevents the cyclicmolecule from being dethreaded from the axle molecule. From a viewpointof bulkiness, however, specific examples thereof can include anadamantyl group, a trityl group, a fluoresceinyl group, a dinitrophenylgroup and a pyrenyl group. In particular, in view of ease ofintroduction, specific examples thereof can include an adamantyl group.

A molecular weight of the axle molecule described above is notparticularly limited, but if the molecular weight is excessively large,compatibility with other components tends to be deteriorated, and if themolecular weight is excessively low, mobility of the cyclic moleculetends to be reduced and the photochromism tends to be reduced. From sucha viewpoint, a weight average molecular weight (Mw) of the axle moleculeis in the range preferably from 1,000 to 100,000, particularly from5,000 to 80,000, and particularly preferably from 10,000 to 50,000.

Moreover, the cyclic molecule has a ring having a size capable ofclathrating the axle molecule as described above, and specific examplesof such a ring can include a cyclodextrin ring, a crown ether ring, abenzocrown ring, a dibenzocrown ring and a dicyclohexanocrown ring, anda cyclodextrin ring is particularly preferable.

In addition, the cyclodextrin ring has an α-form (ring inner diameter:0.45 to 0.6 nm), a β-form (ring inner diameter: 0.6 to 0.8 nm) and aγ-form (ring inner diameter: 0.8 to 0.95 nm). In the present embodiment,however, an α-cyclodextrin ring and a γ-cyclodextrin ring areparticularly preferable, and an α-cyclodextrin ring is most preferable.

With regard to the cyclic molecule having the ring as described above, aplurality of the cyclic molecules clathrate one axle molecule. Ingeneral, when the maximum clathration number of the cyclic moleculeswhich can form clathration per one axle molecule is taken as 1, theclathration number of the cyclic molecules is in the range preferablyfrom 0.001 to 0.6, further preferably from 0.002 to 0.5, and stillfurther preferably from 0.003 to 0.4. If the clathration number of thecyclic molecules is excessively large, the cyclic molecules thicklyexist relative to one axle molecule, and therefore the movability of thecyclic molecules is reduced and the photochromism tends to be reduced.Moreover, if the clathration number thereof is excessively small, theclearance between the axle molecules is narrowed, resulting in reducingthe clearance in which the reversible reaction of the photochromiccompound molecule is allowable, and the photochromism tends to bereduced as well.

In addition, the maximum clathration number of the cyclic moleculesrelative to one axle molecule can be calculated from a length of theaxle molecule and a thickness of the ring of the cyclic molecule.

To take an example of a case where the chain portion of the axlemolecule is formed of polyethylene glycol and the ring of the cyclicmolecule is the a-cyclodextrin ring, for example, the maximumclathration number thereof can be calculated as described below.

More specifically, an equivalent to two repeating units [—CH₂—CH₂O—] ofthe polyethylene glycol is approximated to a thickness of onea-cyclodextrin ring. Accordingly, the number of repeating units iscalculated from a molecular weight of this polyethylene glycol, and onehalf of this number of repeating units is determined as the maximumclathration number of the cyclic molecules. This maximum clathrationnumber is taken as 1.0, and the clathration number of the cyclicmolecules is to be adjusted within the range described above.

Moreover, in the polyrotaxane according to Aspect II, the side chain isa side chain having a group represented by the following formula (1):

-A   (1)

(where, A is an organic group having 1 to 10 carbon atoms, and containsat least one hydroxyl group), in which a pKa of a hydroxyl group of acompound represented by the following formula (2):

H-A   (2)

is 6 or more and less than 14.

In addition, as a matter of course, H in the formula (2) described aboverepresents a hydrogen atom.

As A in the formula (1), an organic group having 1 to 10 carbon atoms,and a group represented by the following formula (A-1) or (A-2) can bepreferably used.

(where, R⁷ is a group selected from a hydrocarbon group having 1 to 4carbon atoms, a halogen atom, a nitro group, an acyl group, amethylsulfonyl group, a trifluoromethyl group, a cyano group and acarboxyl group; p is an integer from 0 to 4; and when the number of R⁷is two or more, R⁷ may be a different group from each other; and R⁸ is atrifluoromethyl group or hydrogen.).

The group represented by (A-1) is most preferably a group in which p is0. Moreover, as the group represented by (A-1), a group represented by(A-1′) is preferable.

In the polyrotaxane according to Aspect II, the compound represented bythe formula (2) is a compound having a structure formed by substituting,for hydrogen, the atom in the bonding site at which the grouprepresented by the formula (1) is bonded with the side chain, in whichthe pKa of the compound represented by the formula (2) is 6 or more andless than 14.

Moreover, with regard to the side chain having the secondary or tertiaryhydroxyl group in the polyrotaxane according to Aspect I, the side chainpreferably has the secondary or tertiary hydroxyl group and ispreferably formed by repetition of organic chains in which the number ofcarbon atoms is within the range from 3 to 20. As the side chain in thepolyrotaxane according to Aspect II, the side chain preferably has thegroup represented by -A and is preferably formed by repetition of theorganic chains in which the number of carbon atoms is within the rangefrom 3 to 20.

A weight average molecular weight of such a side chain is in the rangefrom 200 to 10,000, preferably from 250 to 5,000, and further preferablyfrom 300 to 1,500. More specifically, if the side chain is excessivelysmall, a function of securing the clearance in which the reversiblereaction of the photochromic compound molecule is allowable becomesinsufficient. If the side chain is excessively large, compatibility withother monomers, to be described later, is deteriorated to easily causethe phase separation. Moreover, it becomes difficult to densely mix thephotochromic compound, to be described later, in the polyrotaxane andeventually tends to be difficult in sufficiently utilizing the space tobe secured by the polyrotaxane.

Further, in the polyrotaxane according to Aspect I, the polyrotaxane mayhave the primary hydroxyl group in the side chain. From the viewpoint ofthe moldability, however, when the total mole number of the primary,secondary and tertiary hydroxyl groups in the side chain is taken as100%, a proportion of the primary hydroxyl group is preferably 50% orless, further preferably 20% or less, and most preferably 0%. Morespecifically, the reason is that, if the primary hydroxyl group is lowin amount, the reactivity of the polyrotaxane with the iso(thio)cyanateis reduced, and the moldability is improved.

The side chain having the secondary or tertiary hydroxyl group asdescribed above is introduced thereinto by using a functional group ofthe ring of the cyclic molecule and modifying this functional group. Forexample, the α-cyclodextrin ring has eighteen hydroxyl groups as thefunctional group, and the side chain is introduced thereinto throughthis hydroxyl group. More specifically, a maximum of up to eighteen sidechains can be introduced into one α-cyclodextrin ring. In the presentinvention, in order to sufficiently develop the function of the sidechain described above, 6% or more, and particularly 30% or more of thetotal number of functional groups of such a ring is preferably modifiedwith the side chain. More specifically, 6% or more and 100% or less ofthe total number of functional groups are preferably modified with theside chain, 30% or more and 100% or less of the total number offunctional groups are further preferably modified with the side chain,and 30% or more and 80% or less of the total number of functional groupsare still further preferably modified with the side chain. Incidentally,when the side chains are bonded with nine hydroxyl groups among theeighteen hydroxyl groups in the α-cyclodextrin ring, a degree ofmodification therewith is deemed to be 50% (namely, 0.5).

In the polyrotaxane according to Aspect I, as long as the side chain(the organic chain) as described above has the secondary or tertiaryhydroxyl group, and further a size of the side chain is within the rangedescribed above, the side chain may have the straight chain or branchedchain. The side chain having an appropriate size can be introducedthereinto by using ring-opening polymerization; radical polymerization;cationic polymerization; anionic polymerization; and living radicalpolymerization such as atom transfer radical polymerization, RAFTpolymerization and NMP polymerization, and by reacting an appropriatecompound with the functional group of the ring. When the side chain hasneither the secondary hydroxyl group nor the tertiary hydroxyl groupupon introducing the side chain by polymerization, a reaction only needsto be performed so that the polyrotaxane may have such a structure atthe end of the side chain. Although the details will be described later,for example, if the hydroxyl group introduced into the side chain is theprimary hydroxyl group, the side chain into which the secondary ortertiary hydroxyl group is introduced can be obtained by reacting, withthe primary hydroxyl group of the side chain, the isocyanate compound inwhich the secondary or tertiary hydroxyl group is protected, and thendeprotecting the resulting material.

As a preferred structure of the side chain, the polyrotaxane mostpreferably has a side chain represented by the following formula (1):

In the formula (1), Q is formed of at least one kind selected fromstructures represented by the following formulas (Q-1), (Q-2) and (Q-3).

(where, G is a straight-chain alkylene group or alkenylene group having1 to 8 carbon atoms; a branched-chain alkylene group or alkenylene grouphaving 3 to 20 carbon atoms; an alkylene group or alkenylene groupformed by replacement of a part of the alkylene group or alkenylenegroup by a —O— bond, a —NH— bond, a —SO— bond or a —SiO— bond; or analkylene group formed by replacement of a part of hydrogen of thealkylene group by at least one kind selected from the group consistingof a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, ahalogen atom and an olefin group, and when a plurality of G exist, eachG may be a same group or a different group, and n₁, n₂ and n₃ are eachindependently an integer from 1 to 200), and

when Q is formed of two or more kinds selected from the formulas (Q-1),(Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may be a same group or adifferent group, a total of n₁, n₂ and n₃ is an integer from 1 to 200,and R¹ and R² are each independently a group selected from hydrogen, astraight-chain alkyl group having 1 to 6 carbon atoms or abranched-chain alkyl group having 1 to 6 carbon atoms, excluding a groupin which R¹ and R² are simultaneously hydrogen.

Moreover, as a preferred structure of the side chain, the polyrotaxanemost preferably has a side chain represented by the following formula(1′) as well:

In the formula (1′), Q is formed of at least one kind selected fromstructures represented by the following formulas (Q-1), (Q-2) and (Q-3).

(where, G is a straight-chain alkylene group or alkenylene group having1 to 8 carbon atoms; a branched-chain alkylene group or alkenylene grouphaving 3 to 20 carbon atoms; an alkylene group or alkenylene groupformed by replacement of a part of the alkylene group or alkenylenegroup by a —O— bond, a —NH— bond, a —SO— bond or a —SiO— bond; or analkylene group formed by replacement of a part of hydrogen of thealkylene group by at least one kind selected from the group consistingof a hydroxyl group, a carboxyl group, an acyl group, a phenyl group, ahalogen atom and an olefin group, and when a plurality of G exist, eachG may be a same group or a different group, and n₁, n₂ and n₃ are eachindependently and integer from 1 to 200), and

when Q is formed of two or more kinds selected from the formulas (Q-1),(Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may be a same group or adifferent group, a total of n₁, n₂ and n₃ is an integer from 1 to 200, Xis an alkylene group or alkenylene group having 2 to 20 carbon atoms, oran alkylene group or alkenylene formed by replacement of a part of thealkylene group or alkenylene group by a —O— bond or a —NH— bond, and R³and R⁴ are each independently selected from hydrogen, a straight-chainalkyl group having 1 to 6 carbon atoms or a branched-chain alkyl grouphaving 1 to 6 carbon atoms, excluding a group in which R³ and R⁴ aresimultaneously hydrogen; and R⁵ is carbon or sulfur.

Further, in the polyrotaxane according to Aspect II, the polyrotaxanemay have the hydroxyl group the pKa of which is less than 6 or 14 ormore in the side chain. From the viewpoint of the moldability, however,when the total mole number of the hydroxyl groups in the side chain istaken as 100%, a proportion of the hydroxyl group the pKa of which isless than 6 and 14 or more is preferably 50% or less, further preferably20% or less, and most preferably 0%. More specifically, the reason isthat, if the hydroxyl group the pKa of which is less than 6 and 14 ormore is low in amount, the reactivity with the iso(thio)cyanate can beeasily controlled, the rate of polymerization can be adjusted, and themoldability or the cloudiness described above can be suppressed.

The side chain having the hydroxyl group the pKa of which is 6 or moreand less than 14 is introduced thereinto by using the functional groupof the ring of the cyclic molecule and modifying the functional group.For example, the α-cyclodextrin ring has eighteen hydroxyl groups as thefunctional group, and the side chain is introduced thereinto through thehydroxyl group. More specifically, the maximum of up to eighteen sidechains can be introduced into one α-cyclodextrin ring. In the presentinvention, in order to sufficiently develop the function of the sidechain described above, 6% or more, and particularly 30% or more of thetotal number of the functional groups of such a ring is preferablymodified with the side ring. More specifically, 6% or more and 100% orless of the total number of the functional groups are preferablymodified with the side chain, 30% or more and 100% or less of the totalnumber of functional groups are further preferably modified with theside chain, and 30% or more and 80% or less of the total number of thefunctional groups are still further preferably modified with the sidechain. Incidentally, when the side chains are bonded with nine hydroxylgroups among the eighteen hydroxyl groups of the α-cyclodextrin ring,the degree of modification therewith is deemed to be 50% (namely, 0.5).

In the polyrotaxane according to Aspect II, as long as the side chain(the organic chain) as described above has the hydroxyl group the pKa ofwhich is 6 or more and less than 14, and further the size of the sidechain is within the range described above, the side chain may have thestraight chain or branched chain. The side chain having an appropriatesize can be introduced thereinto by using ring-opening polymerization;radical polymerization; cationic polymerization; anionic polymerization;and living radical polymerization such as atom transfer radicalpolymerization, RAFT polymerization and NMP polymerization, and byreacting an appropriate compound with the functional group of the ring.When the side chain has no hydroxyl group the pKa of which is 6 or moreand less than 14 upon introducing the side chain by polymerization, areaction only needs to be further performed so that the polyrotaxane mayhave a structure in which the hydroxyl group the pKa of which is 6 ormore and less than 14 is introduced into the side chain. Although thedetails will be described later, for example, when the pKa of thehydroxyl group introduced into the side chain is less than 6 or 14 ormore, the side chain into which the hydroxyl group the pKa of which is 6or more and less than 14 is introduced can be obtained by reacting, withthe hydroxyl group in the side chain, the compound having the hydroxylgroup the pKa of which is 6 or more and less than 14 or the compound inwhich the hydroxyl group the pKa of which is 6 or more and less than 14is protected.

As a preferred structure of the side chain, a side chain represented bythe following formula (3) is most preferably introduced thereinto.

-Q-A   (3)

In the formula (3), Q is formed of at least one kind selected fromstructures represented by the following formulas (Q-1), (Q-2) and (Q-3).

(where, G is a straight-chain alkylene group or alkenylene group having1 to 8 carbon atoms; a branched-chain alkylene group or alkenylene grouphaving 3 to 20 carbon atoms; an alkylene group or alkenylene groupformed by replacement of a part of the alkylene group or alkenylenegroup by a —O— bond, a —NH— bond, a —SO— bond or a —SiO— bond; or analkylene group formed by replacement of a part of hydrogen of thealkylene group by at least one kind selected from the group consistingof a carboxyl group, an acyl group, a phenyl group, a halogen atom andan olefin group, and when a plurality of G exist, each G may be a samegroup or a different group, and n₁, n₂ and n₃ are each independently aninteger from 1 to 200), and

when Q is formed of two or more kinds selected from the formulas (Q-1),(Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may be a same group or adifferent group, a total of n₁, n₂ and n₃ is an integer from 1 to 200,and A is an organic group having 1 to 10 carbon atoms and contains atleast one hydroxyl group. In addition, the pKa of the hydroxyl group ofthe compound represented by H-A is 6 or more and less than 14.

As a preferred structure of the side chain, a side chain represented bythe following formula (3′) is most preferably introduced thereinto.

In the formula (3′), Q is formed of at least one kind selected fromstructures represented by the following formulas (Q-1), (Q-2) and (Q-3).

(where, G is a straight-chain alkylene group or alkenylene group having1 to 8 carbon atoms; a branched-chain alkylene group or alkenylene grouphaving 3 to 20 carbon atoms; an alkylene group or alkenylene groupformed by replacement of a part of the alkylene group or alkenylenegroup by a —O— bond, a —NH— bond, a —SO— bond or a —SiO— bond; or analkylene group formed by replacement of a part of hydrogen of thealkylene group by at least one kind selected from the group consistingof a carboxyl group, an acyl group, a phenyl group, a halogen atom andan olefin group, and when a plurality of G exist, each G may be a samegroup or a different group, and n₁, n₂ and n₃ are each independently aninteger from 1 to 200), and

when Q is formed of two or more kinds selected from the formulas (Q-1),(Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may be a same group or adifferent group, a total of n₁, n₂ and n₃ is an integer from 1 to 200,and R⁶ is carbon or sulfur, X is an alkylene group or alkenylene grouphaving 2 to 20 carbon atoms; or an alkylene group or alkenylene groupformed by replacement of a part of the alkylene group or alkenylenegroup by a —O— bond, or a —NH— bond, and A is an organic group having 1to 10 carbon atoms and contains at least one hydroxyl group.

In the preferred structure of the side chain represented by the formula(1), Q has either a structure represented by the formula (Q-1) or astructure represented by the formula (Q-2) or both the structures, andni and n2 are each independently in the range from 1 to 100, and in therange from 1 to 100 in total, further preferably, Q has either astructure represented by the formula (Q-1) or a structure represented bythe formula (Q-2) or both the structures, and n₁ and n₂ are eachindependently in the range from 1 to 75, and in the range from 1 to 75in total, and most preferably, Q has a structure represented by theformula (Q-1), and n₁ is in the range from 1 to 50.

In the polyrotaxane according to Aspect I, as the method for introducingthe side chain having the secondary or tertiary hydroxyl group thereintoas described above, the side chain is preferably introduced thereinto bythe ring-opening polymerization, and as the ring-opening polymerization,the side chain derived from the cyclic compound such as the cyclicether, cyclic siloxane, cyclic lactone, cyclic lactam, cyclic acetal,cyclic amine or cyclic carbonate can be introduced thereinto. When theend is the primary hydroxyl group upon being introduced thereinto, theprimary hydroxyl group only needs to be changed to the secondary ortertiary hydroxyl group according to the technique as described above.

Among these compounds, from viewpoints of ease of availability, highreactivity, and ease of adjustment of the size (molecular weight),cyclic ether, cyclic lactone, cyclic lactam, or cyclic carbonate ispreferably used. If the ring-opening polymerization is performed byusing such a compound, the hydroxyl group can be introduced into theend, but a category of the hydroxyl group at the end is determined by astructure of the compound used. When the hydroxyl group of the sidechain introduced thereinto is the primary hydroxyl group, the secondaryor tertiary hydroxyl group may be introduced thereinto according to thetechnique described above. Specific examples of the cyclic ether, thecyclic lactone, the cyclic lactam and the cyclic carbonate which may bethe side chain are described below.

Cyclic ether from which the primary hydroxyl group may be introducedinto the side chain by the ring-opening polymerization:

ethylene oxide, 1,2-propylene oxide and oxetane.

Cyclic ether from which the secondary or tertiary hydroxyl group may beintroduced into the side chain by the ring-opening polymerization:

epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxideand isobutylene oxide.

Cyclic lactone from which the primary hydroxyl group may be introducedinto the side chain by the ring-opening polymerization:

β-propiolactone, γ-butyrolactone, α-hexyl-γ-butyrolactone,α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone,α-methylene-γ-butyrolactone, α,α-dimethyl-γ-butyrolactone,α-methyl-γ-butyrolactone, γ-nonanolactone, γ-undecanolactone,γ-valerolactone, α-bromo-γ-butyrolactone, γ-crotonolactone,α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone,β-methacryloyloxy-γ-butyrolactone, δ-valerolactone,α-methyl-δ-valerolactone, α-ethyl-δ-valerolactone,α-hexyl-δ-valerolactone, 1,4-dioxan-2-one, 1,5-dioxepan-2-one,ε-caprolactone, α-methyl-ε-caprolactone, α-ethyl-ε-caprolactone,α-hexyl-ε-caprolactone, 5-n-propyl-ε-caprolactone,5-n-hexyl-ε-caprolactone and ζ-enantholactone.

Cyclic lactone from the secondary or tertiary hydroxyl group may beintroduced into the side chain by the ring-opening polymerization:

β-methylpropiolactone, γ-hexanolactone, γ-heptanolactone,γ-octanolactone, γ-decanolactone, γ-dodecanolactone,γ-methyl-γ-decanolactone, DL-pantolactone, δ-hexanolactone, 67-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone,δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone,α,ε-dimethyl-ε-caprolactone and 7α-nonyloxepan-2-one.

Cyclic lactam from which the primary hydroxyl group may be introducedinto the side chain by the ring-opening polymerization:

ε-caprolactam, γ-butyrolactam and DL-α-amino-ε-caprolactam.

Cyclic carbonate from which the primary hydroxyl group may be introducedinto the side chain by the ring-opening polymerization:

ethylene carbonate and vinylene carbonate.

Cyclic carbonate from which the secondary hydroxyl group may beintroduced into the side chain by the ring-opening polymerization:

propylene carbonate and 1,2-butylene carbonate.

The cyclic compounds described above can be used not only alone but alsoin combination with a plurality of kinds.

In the polyrotaxane according to Aspect I, a compound further preferablyused for the ring-opening polymerization is cyclic lactone and cycliclactam. Among these compounds, a compound preferably used is lactonesuch as ε-caprolactone, α-acetyl-γ-butyrolactone,α-methyl-γ-butyrolactone, γ-butyrolactone, γ-valerolactone,ε-caprolactam and γ-butyrolactam. In view of simplicity of synthesis andease of control of the molecular weight, the side chain is mostpreferably ε-caprolactone or ε-caprolactam. In addition, if the sidechain is introduced thereinto by using γ-valerolactone in the compounds,the polyrotaxane having the side chain in which the secondary hydroxylgroup is introduced into the end of the side chain can be obtained. Whena group introduced thereinto after the ring-opening polymerization isthe primary hydroxyl group, also as described above, for example, thesecondary or tertiary hydroxyl group only needs to be introducedthereinto by reacting the primary hydroxyl group with the isocyanatecompound in which the secondary or tertiary hydroxyl group is protected,and then deprotecting the resulting material.

In the polyrotaxane according to Aspect II, as the method forintroducing the side chain having the hydroxyl group the pKa of which is6 or more and less than 14 as described above, the side chain ispreferably introduced thereinto by the ring-opening polymerization, andas the ring-opening polymerization, the side chain derived from thecyclic compound of cyclic ether, cyclic siloxane, cyclic lactone, cycliclactam, cyclic acetal, cyclic amine and cyclic carbonate can beintroduced thereinto.

Among these compounds, from the viewpoints of ease of availability, highreactivity and further ease of adjustment of the size (molecularweight), cyclic ether, cyclic lactone, cyclic lactam or cyclic carbonateis preferably used. If the ring-opening polymerization is performed byusing such a compound, the hydroxyl group can be introduced into theend, but the pKa of the hydroxyl group at the end is determined by thestructure of the compound used. When the pKa of the hydroxyl group ofthe side chain introduced thereinto is less than 6 or 14 or more, thehydroxyl group the pKa of which is 6 or more and less than 14 only needsto be introduced thereinto according to the technique described above.Specific examples of the cyclic ether, the cyclic lactone, the cycliclactam and the cyclic carbonate which may be the side chain aredescribed below.

Cyclic ether:

ethylene oxide, 1,2-propylene oxide, oxetane, epichlorohydrin,epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide and isobutyleneoxide.

Cyclic lactone:

β-propiolactone, γ-butyrolactone, α-hexyl-γ-butyrolactone,α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone,α-methylene-γ-butyrolactone, α,α-dimethyl-γ-butyrolactone,α-methyl-γ-butyrolactone, γ-nonanolactone, γ-undecanolactone,γ-valerolactone, α-bromo-γ-butyrolactone, γ-crotonolactone,α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone,β-methacryloyloxy-γ-butyrolactone, δ-valerolactone,α-methyl-δ-valerolactone, α-ethyl-δ-valerolactone,α-hexyl-δ-valerolactone, 1,4-dioxan-2-one, 1,5-dioxepan-2-one,ε-caprolactone, α-methyl-ε-caprolactone, α-ethyl-ε-caprolactone,α-hexyl-ε-caprolactone, 5-n-propyl-ε-caprolactone,5-n-hexyl-ε-caprolactone, ζ-enantholactone, β-methylpropiolactone,γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-decanolactone,γ-dodecanolactone, γ-methyl-γ-decanolactone, DL-pantolactone,δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone,δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone,δ-tetradecanolactone, α,ε-dimethyl-ε-caprolactone and7α-nonyloxepan-2-one.

Cyclic lactam: ε-caprolactam, γ-butyrolactam andDL-α-amino-ε-caprolactam.

Cyclic carbonate: ethylene carbonate, vinylene carbonate, propylenecarbonate and 1,2-butylene carbonate.

The cyclic compounds described above can be used not only alone but alsoin combination with a plurality of kinds.

In the polyrotaxane according to Aspect II, a compound furtherpreferably used for the ring-opening polymerization is cyclic lactoneand cyclic lactam. Among these compounds, a compound preferably used islactone such as ε-caprolactone, α-acetyl-γ-butyrolactone,α-methyl-γ-butyrolactone, γ-butyrolactone, γ-valerolactone,ε-caprolactam and γ-butyrolactam. In view of simplicity of synthesis andease of control of the molecular weight, the side chain is mostpreferably ε-caprolactone or ε-caprolactam. When the hydroxyl group thepKa of which is less than 6 or 14 or more is introduced thereinto afterpolymerization in the side chain, also as described above, for example,the hydroxyl group the pKa of which is 6 or more and less than 14 onlyneeds to be introduced thereinto by reacting the hydroxyl group with theisocyanate compound in which the hydroxyl group the pKa of which is 6 ormore and less than 14 is protected, and then deprotecting the resultingmaterial.

Thus, when the side chain is introduced thereinto by reacting the cycliccompound therewith by the ring-opening polymerization, the functionalgroup (for example, the hydroxyl group) bound to the ring has poorreactivity, and has difficulty in directly reacting a large moleculetherewith particularly by steric hindrance or the like in several cases.In such a case, for example, the production method can employ a means inwhich, in order to react caprolactone or the like therewith, thefunctional group (hydroxyl group) enriched with reactivity is introducedthereinto by performing hydroxypropylation by reacting a lowmolecular-weight compound such as propylene oxide with the functionalgroup, and then the side chain is introduced thereinto by thering-opening reaction using the cyclic compound described above.

Further, as the production method for the polyrotaxane beingcharacterized in that the side chain having the secondary or tertiaryhydroxyl group is introduced into at least part of the cyclic molecule(polyrotaxane according to Aspect I) according to the present invention,in view of simplicity of synthesis and ease of control of the molecularweight, the production method preferably includes reacting, with acompound represented by the following formula (2), a polyrotaxane havinga composite molecular structure formed of an axle molecule and aplurality of cyclic molecules clathrating the axle molecule, and thepolyrotaxane in which a side chain having a primary hydroxyl group isintroduced into at least part of the cyclic molecule of thepolyrotaxane. Moreover, the production method most preferably includesreacting, with the compound represented by the following formula (2),the polyrotaxane in which the side chain having the primary hydroxylgroup is introduced into at least part of the cyclic molecule of thepolyrotaxane, and then deprotecting Z.

(where, X is an alkylene group or alkenylene group having 2 to 20 carbonatoms, or an alkylene group or alkenylene group formed by replacement ofa part of the alkylene group or alkenylene group by a —O— bond or a —NH—bond; Z is a group selected from the group consisting of the followingformulas Z-1 to Z-9; R³ and R⁴ are each independently selected fromhydrogen, a straight-chain alkyl group having 1 to 6 carbon atoms or abranched-chain alkyl group having 1 to 6 carbon atoms, excluding a groupin which R³ and R⁴ are simultaneously hydrogen; and R⁵ is carbon orsulfur.).

The alkylene group may be a branched-chain alkylene group orstraight-chain alkylene group. Moreover, the alkenylene group may be abranched-chain alkenylene group or straight-chain alkenylene group.

Specific examples of the compound represented by the formula (2)include: 2-methyl-2-(trimethylsiloxy)propyl isocyanate,2-methyl-2-(t-butyldimethylsiloxy)propyl isocyanate,2-(trimethylsiloxy)propyl isocyanate, 2-(t-butyldimethylsiloxy)propylisocyanate, [(2-isocyanato-1,1-dimethylethoxy)methyl]benzene and(2-isocyanato-1-methylpropoxy)benzene, and particularly preferablyinclude: 2-methyl-2-(trimethylsiloxy)propyl isocyanate and2-methyl-2-(t-butyldimethylsiloxy)propyl isocyanate.

As the production method including reacting, with the compoundrepresented by the following formula (2), the polyrotaxane in which theside chain having the primary hydroxyl group is introduced into at leastpart of the cyclic molecule, and then deprotecting Z, the followingmethod can be employed.

The polyrotaxane in which the side chain having the tertiary hydroxylgroup is introduced into at least part of the cyclic molecule can beobtained by preparing the polyrotaxane having the primary hydroxyl groupin the side chain, according to the method described in Patentliterature 8, and introducing 2-methy-2-(trimethylsiloxy)propylisocyanate into the primary hydroxyl group of the polyrotaxane, and thendeprotecting the resulting material by using tetra-n-butylammoniumfluoride (TBAF). When the secondary hydroxyl group is introducedthereinto according to the production method described above,2-(trimethylsiloxy)propyl isocyanate or 2-(t-butyldimethylsiloxy)propylisocyanate only needs to be used in place of2-methyl-2-(trimethylsiloxy)propyl isocyanate.

In the polyrotaxane according to Aspect I, as the polyrotaxane mostpreferably used, a polyrotaxane in which polyethylene glycol havingadamantyl groups bound at both ends is applied as an axle molecule, anda cyclic molecule having an a-cyclodextrin ring is applied as a ring,and a side chain is further introduced into the ring byE-polycaprolactone, and a secondary or tertiary hydroxyl group isintroduced into an end according to the production method describedabove is preferably used.

Further, as the production method for the polyrotaxane beingcharacterized in that the side chain having the hydroxyl group the pKaof which is 6 or more and less than 14 is introduced into at least partof the cyclic molecule (polyrotaxane according to Aspect II) accordingto the present invention, in view of simplicity of synthesis and ease ofcontrol of the molecular weight, the production method preferablyincludes reacting, with a compound represented by the following formula(4), a polyrotaxane having a composite molecular structure formed of anaxle molecule and a plurality of cyclic molecules clathrating the axlemolecule, and the polyrotaxane in which a side chain having a primaryhydroxyl group a pKa of which is 14 or more is introduced into at leastpart of the cyclic molecule of the polyrotaxane. Moreover, theproduction method most preferably includes reacting, with the compoundrepresented by the following formula (4), the polyrotaxane in which theside chain having the primary hydroxyl group the pKa of which is 14 ormore is introduced into at least part of the cyclic molecule of thepolyrotaxane, and then deprotecting Z.

[Formula 11]

O═R⁶═N—X—T—O—Z   (4)

[where, R⁶ is carbon or sulfur, X is an alkylene group or alkenylenegroup having 2 to 20 carbons, or an alkylene group or alkenylene groupformed by replacement of a part of the alkylene group or alkenylenegroup by a —O— bond or a —NH— bond, where, T is a group selected fromthe group consisting of the following formulas (T-1) or (T-2):

(where, R⁷ is a group selected from a hydrocarbon group having 1 to 4carbon atoms, a halogen atom, a nitro group, an acyl group, amethylsulfonyl group, a trifluoromethyl group, a cyano group and acarboxyl group; p is an integer from 0 to 4; and when the number of R⁷is two or more, R⁷ may be a different group from each other, R⁸ is atrifluoromethyl group or hydrogen), and where, Z is a group selectedfrom the group consisting of the following formulas Z-1 to Z-9]:

The group represented by (T-1) is most preferably a group in which p is0.

The alkylene group may be a branched-chain alkylene group orstraight-chain alkylene group. Moreover, the alkenylene group may be abranched-chain alkenylene group or straight-chain alkenylene group.

Specific examples of the compound represented by the formula (4)include: 1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene,1-(2-isothiocyanateethyl)-4-[(trimethylsilyl)oxy]-benzene,1-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-4-(2-isocyanatepropyl)benzene,1-(2-isocyanatoethyl)-4-methoxybenzene,1-(2-isocyanatoethyl)-4-(phenylmethoxy)-benzene,3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneisocyanate, 4,4,4-trifluoro-3-(phenylmethoxy)-1-butane isocyanate and4,4,4-trifluoro-3-[(4-methoxyphenyl)methoxy]-1-butane isocyanate. Inaddition,3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneisocyanate, 4,4,4-trifluoro-3-(phenylmethoxy)-1-butane isocyanate or4,4,4-trifluoro-3-[(4-methoxyphenyl)methoxy]-1-butane isocyanate can beobtained by converting a primary amine group into an isocyanate group byreacting, with phosgene, the primary amine group of3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneamine,4,4,4-trifluoro-3-(phenylmethoxy)-1-butaneamine or4,4,4-trifluoro-3-[(4-methoxyphenyl)methoxy]-1-butaneamine.

As the production method including reacting, with the compoundrepresented by the formula (4), the polyrotaxane in which the side chainhaving the primary hydroxyl group the pKa of which is 14 or more isintroduced into at least part of the cyclic molecule, and thendeprotecting Z, the method as described below can be employed.

The polyrotaxane in which the side chain having the hydroxyl group thepKa of which is 6 or more and less than 14 is introduced into at leastpart of the cyclic molecule can be obtained by preparing thepolyrotaxane having the hydroxyl group the pKa of which is 14 or more inthe side chain, according to the method described in Patent literature8, and introducing 1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzeneinto the primary hydroxyl group the pKa of which is 14 or more in thepolyrotaxane, and then deprotecting the resulting material by usingtetra-n-butylammonium fluoride (TBAF).

In the polyrotaxane according to Aspect II, as the polyrotaxane mostpreferably used, a polyrotaxane in which polyethylene glycol havingadamantyl groups bound at both ends is applied as an axle molecule, anda cyclic molecule having an α-cyclodextrin ring is applied as a ring,and a side chain is further introduced into the ring byε-polycaprolactone, and a hydroxyl group a pKa of which is 6 or more andless than 14 is introduced into an end according to the productionmethod described above is preferably used.

The polyrotaxane (A) according to the present invention (for example,the polyrotaxane according to Aspect I or Aspect II) can be used as anoptical composition. For example, when the polyrotaxane (A) is usedtogether with a (B) component to be described later to form the opticalcomposition, the optical composition can be preferably used for aplastic lens such as an eyeglass lens.

Next, (B) will be described.

<(B) Compound Having Two or More Groups of at Least One Kind Selectedfrom an Isocyanate Group and an Isothiocyanate Group in One Molecule>

A compound having two or more groups of at least one kind selected froman isocyanate group and an isothiocyanate group in one molecule(hereinafter, also referred to simply as “polyiso(thio)cyanatecompound”) that forms the optical composition according to the presentinvention is a compound having two or more groups (in total) of anisocyanate group and an isothiocyanate group in one molecule of thepolyiso(thio)cyanate compound. Among the polyiso(thio)cyanate compounds,specific examples of the polyisocyanate compound include: aliphaticisocyanate, alicyclic isocyanate, aromatic isocyanate, sulfur-containingaliphatic isocyanate, aliphatic sulfide-based isocyanate, aromaticsulfide-based isocyanate, aliphatic sulfone-based isocyanate, aromaticsulfone-based isocyanate, sulfonate-based isocyanate, aromatic sulfonicacid amide-based isocyanate and sulfur-containing heterocyclic ringisocyanate.

Moreover, specific examples of the polyisothiocyanate compound include:aliphatic isothiocyanate, alicyclic isothiocyanate, aromaticisothiocyanate, heterocyclic ring-containing isothiocyanate, carbonylisothiocyanate, sulfur-containing aliphatic isothiocyanate,sulfur-containing aromatic isothiocyanate and sulfur-containingheterocyclic ring isothiocyanate. Specific examples of thesepolyiso(thio)cyanate compounds can include the compounds describedbelow.

Aliphatic isocyanate; ethylene diisocyanate, trimethylene diisocyanate,tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylenediisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentanediisocyanate, 2,2,4-atrimethylhexamethylene diisocyanate, decamethylenediisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate,2,4,4-trimethylhexamethylene diisocyanate,1,6,11-trimethylundecamethylene diisocyanate,1,3,6-trimethylhexamethylene diisocyanate,1,8-diisocyanato-4-isocyanatomethyloctane,2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane,bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butyleneglycol dipropyl ether-ω,ω′-diisocyanate, lysine diisocyanatomethylester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatehexanoate and 2-isocyanatopropyl-2,6-diisocyanate hexanoate.

Alicyclic isocyanate: isophorone diisocyanate,(bicyclo[2,2,1]heptane-2,5-diyl)bismethylene diisocyanate,(bicyclo[2,2,1]heptane-2,6-diyl)bismethylene diisocyanate,2β,5α-bis(isocyanato)norbornane, 2β,5β-bis(isocyanato)norbornane,2β,6α-bis(isocyanato)norbornane, 2β,6β-bis(isocyanato)norbornane,2,6-di(isocyanatomethyl)furan, bis(isocyanatomethyl)cyclohexane,dicyclohexylmethane diisocyanate, 4,4-isopropylidenebis(cyclohexylisocyanate), cyclohexane diisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethane diisocyanate,2,2′-dimethyldicyclohexylmethane diisocyanate,bis(4-isocyanato-n-butylidene)pentaerythritol, dimer acid diisocyanate,2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane,2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane,2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane,1,3,5-tris(isocyanatomethyl)cyclohexane,3,8-bis(isocyanatomethyl)tricyclodecane,3,9-bis(isocyanatomethyl)tricyclodecane,4,8-bis(isocyanatomethyl)tricyclodecane,4,9-bis(isocyanatomethyl)tricyclodecane, 1,5-diisocyanatodecalin,2,7-diisocyanatodecalin, 1,4-diisocyanatodecalin,2,6-diisocyanatodecalin, a mixture ofbicyclo[4,3,0]nonane-3,7-diisocyanate andbicyclo[4,3,0]nonane-4,8-diisocyanate, a mixture ofbicycle[2,2,1]heptane-2,5-diisocyanate andbicyclo[2,2,1]heptane-2,6-diisocyanate, a mixture ofbicycle[2,2,2]octane-2,5-diisocyanate andbicyclo[2,2,2]octane-2,6-diisocyanate and a mixture oftricycle[5,2,1,0^(2.6)]decane-3,8-diisocyanate andtricyclo[5,2,1,0^(2,6)]decane-4,9-diisocyanate.

Aromatic isocyanate: xylylene diisocyanate (o-, m-, p-),tetrachloro-m-xylylene diisocyanate, 4-chloro-m-xylylene diisocyanate,4,5-dichloro-m-xylylene diisocyanate, 2,3,5,6-tetrabromo-p-xylylenediisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylenediisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene,1,3-bis(a,a-dimethylisocyanatomethyl)benzene,1,4-bis(α,α-dimethylisocyanatomethyl)benzene,α,α,α′,α′-tetramethylxylylene diisocyanate, bis(isocyanatobutyl)benzene,bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether,bis(isocyanatoethyl)phthalate, mesitylene triisocyanate,2,6-di(isocyanatomethyl)furan, phenylene diisocyanate, tolylenediisocyanate, ethylphenylene diisocyanate, isopropylphenylenediisocyanate, dimethylphenylene diisocyanate, diethylphenylenediisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzene triisocyanate, 1,3,5-triisocyanatomethylbenzene,naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyldiisocyanate, tolidine diisocyanate, 4,4′-diphenylmethane diisocyanate,3,3′-dimethyldiphenylmethane-4,4′-diisocyanate,bibenzyl-4,4′-diisocyanate, bis(isocyanatophenyl)ethylene,3,3′-dimethoxybiphenyl-4,4′-diisocyanate, triphenylmethanetriisocyanate, polymeric MDI, naphthalene triisocyanate,diphenylmethane-2,4,4′-triisocyanate,3-methyldiphenylmethane-4,4′,6-triisocyanate,4-methyl-diphenylmethane-2,3,4′,5,6-pentaisocyanate,phenylisocyanatomethyl isocyanate, phenylisocyanatoethyl isocyanate,tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate,hexahydrodiphenylmethane-4,4′-diisocyanate, diphenyl ether diisocyanate,ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycoldiphenyl ether diisocyanate, benzophenone diisocyanate, diethyleneglycol diphenyl ether diisocyanate, dibenzofuran diisocyanate, carbazolediisocyanate, ethylcarbazole diisocyanate and dichlorocarbazolediisocyanate.

Sulfur-containing aliphatic isocyanate: thiodiethyl diisocyanate,thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfonediisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate,1-isocyanatomethylthio-2,3-bis(2-isocyanatoethylthio)propane,1,2-bis(2-isocyanatoethylthio)ethane,1,1,2,2-tetrakis(isocyanatomethylthio)ethane,2,2,5,5-tetrakis(isocyanatomethylthio)-1,4-dithiane,2,4-dithiapentane-1,3-diisocyanate,2,4,6-trithiaheptane-3,5-diisocyanate,2,4,7,9-tetrathiapentane-5,6-diisocyanate,bis(isocyanatomethylthio)phenylmethane,bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane,bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane and1,5-isocyanato-2-isocyanatomethyl-3-thiapentane.

Aliphatic sulfide-based isocyanate:bis[2-(isocyanatomethylthio)ethyl]sulfide,dicyclohexylsulfide-4,4′-diisocyanate, bis(isocyanatomethyl)sulfide,bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide,bis(isocyanatohexyl)sulfide, bis(isocyanatomethyl)disulfide,bis(isocyanatoethyl)disulfide and bis(isocyanatopropyl)disulfide.

Aromatic sulfide-based isocyanate: diphenylsulfide-2,4′-diisocyanate,diphenylsulfide-4,4′-diisocyanate,3,3′-dimethoxy-4,4′-diisocyanatodibenzyl thioether,bis(4-isocyanatomethylbenzene)sulfide, 4,4′-methoxybenzenethioethyleneglycol-3,3′-diisocyanate, diphenyldisulfide-4,4′-diisocyanate,2,2′-dimethyldiphenyldisulfide-5,5′-diisocyanate,3,3′-dimethyldiphenyldisulfide-5,5′-diisocyanate,3,3′-dimethyldiphenyldisulfide-6,6′-diisocyanate,4,4′-dimethyldiphenyldisulfide-5,5′-diisocyanate,3,3′-dimethoxydiphenyldisulfide-4,4′-diisocyanate and4,4′-dimethoxydiphenyldisulfide-3,3′-diisocyanate.

Aliphatic sulfone-based isocyanate: bis(isocyanatomethyl)sulfone.

Aromatic sulfone-based isocyanate: diphenylsulfone-4,4′-diisocyanate,diphenylsulfone-3,3′-diisocyanate, benzylidenesulfone-4,4′-diisocyanate,diphenylmethanesulfone-4,4′-diisocyanate,4-methyldiphenylmethanesulfone-2,4′-diisocyanate,4,4′-dimethoxydiphenylsulfone-3,3′-diisocyanate,3,3′-dimethoxy-4,4′-diisocyanatodibenzyl sulfone,4,4′-dimethyldiphenylsulfone-3,3′-diisocyanate,4,4′-di-tert-butyldiphenylsulfone-3,3′-diisocyanate,4,4′-dimethoxybenzeneethylenedisulfone-3,3′-diisocyanate and4,4′-dichlorodiphenylsulfone-3,3′-diisocyanate.

Sulfonate-based isocyanate:4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester and4-methoxy-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester.

Aromatic sulfonic acid amide-based isocyanate:4-methyl-3-isocyanatobenzenesulfonylanilide-3′ -methyl-4′ -isocyanate,dibenzenesulfonyl-ethylenediamine-4,4′-diisocyanate,4,4′-dimethoxybenzenesulfonyl-ethylenediamine-3,3′-diisocyanate and4-methyl-3-isocyanatobenzensulfonylanilide-4-methyl-3′-isocyanate.

Sulfur-containing heterocyclic ring isocyanate:thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanatomethyl,1,4-dithiane-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanatomethyl,1,3-dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanatomethyl,1,3-dithiolane-2-methyl-4,5-diisocyanatomethyl,1,3-dithiolane-2,2-diisocyanatoethyl,tetrahydrothiophene-2,5-diisocyanate,tetrahydrothiophene-2,5-diisocyanatomethyl,tetrahydrothiophene-2,5-diisocyanatoethyl,tetrahydrothiophene-3,4-diisocyanatomethyl, tricyclothiaoctanediisocyanate, 2-(1,1-diisocyanatomethyl)thiophene,3-(1,1-diisocyanatomethyl)thiophene,2-(2-thienylthio)-1,2-diisocyanatopropane,2-(3-thienylthio)-1,2-diisocyanatopropane,3-(2-thienyl)-1,5-diisocyanato-2,4-dithiapentane,3-(3-thienyl)-1,5-diisocyanato-2,4-dithiapentane,3-(2-thienylthio)-1,5-diisocyanato-2,4-dithiapentane,3-(3-thienylthio)-1,5-diisocyanato-2,4-dithiapentane,3-(2-thienylthiomethyl)-1,5-diisocyanato-2,4-dithiapentane,3-(3-thienylthiomethyl)-1,5-diisocyanato-2,4-dithiapentane,2,5-(diisocyanatomethyl)thiophene, 2,3-(diisocyanatomethyl)thiophene,2,4-(diisocyanatomethyl)thiophene, 3,4-(diisocyanatomethyl)thiophene,2,5-(diisocyanatomethylthio)thiophene,2,3-(dissocyanatomethylthio)thiophene,2,4-(diisocyanatomethylthio)thiophene,3,4-(diisocyanatomethylthio)thiophene and2,4-bisisocyanatomethyl-1,3,5-trithiane.

Further, a halogen-substituted product of the polyisocyanate, analkyl-substituted product thereof, an alkoxy-substituted product thereofor a nitro-substituted product thereof; a prepolymer-type modifiedproduct with polyhydric alcohol; a carbodiimide-modified producttherewith; a urea-modified product therewith; a biuret-modified producttherewith; and a dimerized or trimerized reaction product or the likecan also be used.

Aliphatic isothiocyanate: 1,2-diisothiocyanatoethane,1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane,1,6-diisothiocyanatohexane and p-phenylenediisopropylidenediisothiocyanate.

Alicyclic isothiocyanate: cyclohexyl isothiocyanate, cyclohexanediisothiocyanate, 2,4-bis(isothiocyanatomethyl)norbornane,2,5-bis(isothiocyanatomethyl)norbornane,3,4-bis(isothiocyanatomethyl)norbornane and3,5-bis(isothiocyanatomethyl)norbornane.

Aromatic isothiocyanate: phenyl isothiocyanate,1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene,1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene,2,5-diisothiocyanato-m-xylene diisocyanate,4,4′-diisothiocyanato-1,1′-biphenyl, 1,1′-methylenebis(4-isothiocyanatobenzene), 1,1′-methylenebis(4-isothiocyanato-2-methylbenzene), 1,1′-methylenebis(4-isothiocyanato-3-methylbenzene), 1,1′-(1,2-ethanediyl)bis(4-isothiocyanatobenzene), 4,4′-diisothiocyanato benzophenone,4,4′-diisothiocyanato-3,3′-dimethyl benzophenone,benzanilide-3,4′-diisothiocyanate, diphenylether-4,4′-diisothiocyanateand diphenylamine-4,4′-diisothiocyanate.

Heterocyclic ring-containing isothiocyanate:2,4,6-triisothiocyanato-1,3,5-triazine.

Carbonyl isothiocyanate: hexanediol diisothiocyanate, nonanedioldiisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1-4-benzenedicarbonyl diisothiocyanate and(2,2-bipyridine)-4,4′-dicarbonyl diisothiocyanate.

Further, polyfunctional isothiocyanate having at least one sulfur atomin addition to a sulfur atom of the isothiocyanate group can also beused. Specific examples of such polyfunctional isothiocyanate caninclude the compounds described below.

Sulfur-containing aliphatic isothiocyanate:thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane) anddithiobis(2-isothiocyanatoethane).

Sulfur-containing aromatic isothiocyanate:1-isothiocyanato-4-{(2-isothiocyanato)sulfonyl}benzene,thiobis(4-isothiocyanatobenzene), sulfonylbis(4-isothiocyanatobenzene),sulfinylbis(4-isothiocyanatobenzene),dithiobis(4-isothiocyanatobenzene),4-isothiocyanato-1-{(4-isothiocyanatophenyl)sulfonyl}-2-methoxy-benzene,4-methyl-3-isothiocyanatobenzenesulfonyl-4′-isothiocyanatophenyl esterand4-methyl-3-isothiocyanatobenzenesulfonylanilide-3′-methyl-4′-isothiocyanate.

Sulfur-containing heterocyclic isothiocyanate:thiophene-2,5-diisothiocyanate and 1,4-dithiane-2,5-diisothiocyanate.

<Preferred Examples for (B) Component>

Preferred examples of the polyiso(thio)cyanate compound being the (B)component are preferably selected from pentamethylene diisocyanate,hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylenediisocyanate, isophorone diisocyanate, norbornane diisocyanate,2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane,2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 1,2-bis(2-isocyanatoethylthio)ethane, xylene diisocyanate (o-, m-, p-),2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and4,4′-diphenylmethane diisocyanate, and may be selected from a mixturethereof.

<Preferred Blending Proportion of (A) and (B) Components>

Further, according to the present invention, with regard to an optimumblending proportion of the (A) and (B) components described above forobtaining excellent moldability, mechanical strength and hardness in theoptical article or excellent photochromic characteristics upon addingthe photochromic compound thereto, to be described later, the resultingblend contains preferably (A) in the range from 50 to 97 parts by mass,and (B) in the range from 3 to 50 parts by mass, further preferably (A)in the range from 60 to 95 parts by mass, and (B) in the range from 5 to40 parts by mass, and most preferably (A) in the range from 70 to 93parts by mass, and (B) in the range from 7 to 30 parts by mass, based ona total of 100 parts by mass of the (A) and the (B) described above.

Moreover, in the present invention, in addition to the polyrotaxanebeing the (A) component, an iso(thio)cyanate reactive group-containingcompound (C) in which the group can react with the (B) component can beused. The (C) component will be described below.

<(C) Iso(thio)Cyanate Reactive Group-Containing Compound>Specificexamples of the iso(thio)cyanate reactive group-containing compound caninclude: a poly(thi)ol compound having two or more hydroxyl groupsand/or thiol groups in one molecule (C-1) or a mono(thi)ol compoundhaving one hydroxyl group or thiol group in one molecule (C-2).

<(C-1) Poly(thi)ol Compound Having Two or More Groups of at Least OneKind of Group Selected from a Hydroxyl Group and a Thiol Group in OneMolecule>

A poly(thi)ol compound having two or more groups of at least one kind ofgroup selected from a hydroxyl group and a thiol group in one molecule(hereinafter, also referred to simply as “poly(thi)ol compound”) is acompound having two or more (in total) of at least one kind of groupselected from the hydroxyl group (OH group) and the thiol group (SHgroup) in the poly(thi)ol compound. Among the poly(thi)ol compounds, thepolyol compound is typified, for example, by a di-, tri-, tetra-, penta-or hexa-hydroxy compound, polyester containing two or more OH groups inone molecule (polyester polyol), polyether containing two or more OHgroups in one molecule (hereinafter, referred to as polyether polyol),polycarbonate containing two or more OH groups in one molecule(polycarbonate polyol), polycaprolactone containing two or more OHgroups in one molecule (polycaprolactone polyol) and an acrylic polymercontaining two or more OH groups in one molecule (polyacryl polyol).

Moreover, specific examples of the polythiol compound include: aliphaticpolythiol, aromatic polythiol, halogen-substituted aromatic polythiol,heterocycle-containing polythiol and sulfur atom-containing aromaticpolythiol in addition to a mercapto group, sulfur atom-containingaliphatic polythiol in addition to a mercapto group, and a sulfuratom-containing heterocycle-containing polythiol in addition to amercapto group. Specific examples of these compounds are as describedbelow.

Aliphatic alcohol: ethylene glycol, diethylene glycol, propylene glycol,dipropylene glycol, butylene glycol, 1,5-dihydroxypentane,1,6-dihydroxyhexane, 1,7-dihydroxyheptane, 1,8-dihydroxyoctane,1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane,1,12-dihydroxydodecane, neopentyl glycol, glycerin, trimethylolethane,trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol,dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol,ribitol, arabinitol, xylitol, allitol, mannitol, dulcitol, iditol,glycol, inositol, hexanetriol, triglycerol, diglycerol, triethyleneglycol, polyethylene glycol, tris(2-hydroxyethyl)isocyanurate,cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol,cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol,tricyclo[5,2,1,0^(2,6)]decane-dimethanol, bicyclo[4,3,0]-nonanediol,dicyclohexanediol, tricyclo[5,3,1,1^(36,9)]dodecanediol,bicyclo[4,3,0]nonanedimethanol,tricyclo[5,3,1,1^(3,9)]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1^(3,9)]dodecanol, spiro[3,4]octanediol,butylcyclohexanediol, 1,1′-bicyclohexylidenediol, cyclohexanetriol,maltitol, lactitol, 3-methyl-1,5-dihydroxypentane, dihydroxyneopentyl,2-ethyl-1,2-dihydroxyhexane, 2-methyl-1,3-dihydroxypropane,1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,2-cyclohexanedimethanol, o-dihydroxyxylylene, m-dihydroxyxylylene,p-dihydroxyxylylene, 1,4-bis(2-hydroxyethyl)benzene,1,4-bis(3-hydroxypropyl)benzene, 1,4-bis(4-hydroxybutyl)benzene,1,4-bis(5-hydroxypentyl)benzene, 1,4-bis(6-hydroxyhexyl)benzene,2,2-bis[4-(2″-hydroxyethyloxy)phenyl]propane, as a trifunctional polyol,TMP-30, TMP-60 and TMP-90, manufactured by Nippon Nyukazai Co., Ltd.,and as a tetrafunctional polyol, PNT40 and PNT60, manufactured by NipponNyukazai Co., Ltd.

Aromatic alcohol: dihydroxynaphthalene, trihydroxynaphthalene,tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol,biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol,trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol,tetrabromobisphenol A, bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane,bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)-3-methylbutane,2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane,2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)octane,2,2-bis(4-hydroxyphenyl)-4-methylpentane,2,2-bis(4-hydroxyphenyl)heptane, 4,4-bis(4-hydroxyphenyl)heptane,2,2-bis(4-hydroxyphenyl)tridecane, 2,2-bis(4-hydroxyphenyl)octane,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl) propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl) propane,2,2-bis(3-tert-butyl-4-hydroxyphenyl) propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4′-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,2,2-bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)propane,bis(4-hydroxyphenyl)cyanomethane,1-cyano-3,3-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)cycloheptane,1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane,1,1-bis(3-methyl-4-hydroxyphenyl)-4-methylcyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,2,2-bis(4-hydroxyphenyl)norbornane, 2,2-bis(4-hydroxyphenyl)adamantane,4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenylether, ethylene glycol bis(4-hydroxyphenyl)ether, 4,4′-dihydroxydiphenylsulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide,3,3′-dicyclohexyl-4,4′-dihydroxydiphenyl sulfide,3,3′-diphenyl-4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenylsulfoxide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfoxide,4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, bis(4-hydroxyphenyl)ketone,bis(4-hydroxy-3-methylphenyl)ketone,7,7′-dihydroxy-3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi(2H-1-benzopyran),trans-2,3-bis(4-hydroxyphenyl)-2-butene,9,9-bis(4-hydroxyphenyl)fluorene, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, 4,4′-dihydroxybiphenyl andhydroquinone resorcin.

Sulfur-containing polyol: bis-[4-(hydroxyethoxy)phenyl]sulfide,bis-[4-(2-hydroxypropoxy)phenyl]sulfide,bis-[4-(2,3-dihydroxypropoxy)phenyl]sulfide,bis-[4-(4-hydroxycyclohexyloxy)phenyl]sulfide,bis-[2-methyl-4-(hydroxyethoxy)-6-butylphenyl]sulfide, a compound inwhich three or less molecules (on an average) of ethylenoxide and/orpropylene oxide per one hydroxyl group are added to thesulfur-containing polyol, di-(2-hydroxyethyl)sulfide,bis(2-hydroxyethyl)disulfide, 1,4-dithiane-2,5-diol,bis(2,3-dihydroxypropyl)sulfide, tetrakis(4-hydroxy-2-thiabutyl)methane,bis(4-hydroxyphenyl)sulfone, tetrabromobisphenol S, tetramethylbisphenolS, 4,4′-thiobis(6-tert-butyl-3-methylphenol) and1,3-bis(2-hydroxyethylthioethyl)-cyclohexane.

Sulfur-containing heterocyclic polyol:2,5-bis(hydroxymethyl)-1,4-dithiane,3-hydroxy-6-hydroxymethyl-1,5-dithiacycloheptane and3,7-dihydroxy-1,5-dithiacyclooctane.

Polyester polyol: a compound obtained by a condensation reaction ofpolyol with polybasic acid.

Polyether polyol: a compound obtained by a reaction of a compound havingtwo or more active hydrogen-containing groups in a molecule withalkylene oxide, and a modified product thereof.

Polycaprolactone polyol: a compound obtained by ring-openingpolymerization of ε-caprolactone.

Polycarbonate polyol: a compound obtained by phosgenation of one or morekinds of low molecular-weight polyols, and a compound obtained by atransesterification process using ethylene carbonate, diethyl carbonate,diphenyl carbonate or the like.

Polyacryl polyol: a compound obtained from a copolymer of hydroxylgroup-containing acrylate or methacrylate with a monomer copolymerizablewith the ester.

Aliphatic polythiol: methanedithiol, 1,2-ethanedithiol,1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol,2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol,tetrakis(mercaptomethyl)methane, 1,1-cyclohexanedithiol,1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol,3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol,bicyclo[2,2,1]hepta-exo-cis-2,3-dithiol,1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid bis(2-mercaptoethylester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester),2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol(3-mercaptoacetate), diethylene glycol bis(2-mercaptoacetate),diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methylether, 2,3-dimercaptopropyl methyl ether,2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl)ether,ethylene glycol bis(2-mercaptoacetate), ethylene glycolbis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane,1,4-butanediol bis(3-mercaptopropionate), 1,4-butanediolbis(thioglycolate), 1,6-hexanediol bis(thioglycolate), tetraethyleneglycol bis(3-mercaptopropionate), trimethylolpropanetris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate),trimethylolethane tris(3-mercaptobutyrate), trimethylolpropanetris(3-mercaptobutyrate), pentaerythritol tetrakis(2-mercaptoacetate),pentaerythritol tetrakis(3-mercaptopropionate),1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, dipentaerythritolhexakis(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane,trimethylolpropane tris(3-mercaptobutyrate), trimethylolethanetris(3-mercaptobutyrate),1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,2-mercaptomethyl-1,3-propanedithiol, 2-mercaptomethyl-1,4-butanedithiol,2,4,5-tris(mercaptomethyl)-1,3-dithiolane,2,2-bis(mercaptomethyl)-1,4-butanedithiol,4,4-bis(mercaptomethyl)-3,5-dithiaheptane-1,7-dithiol,2,3-bis(mercaptomethyl)-1,4-butanedithiol, 2,6-bis(mercaptomethyl)-3,5-dithiaheptane-1,7-dithiol,4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,2,5-bismercaptomethyl-1,4-dithiane,1,1,3,3-tetrakis(mercaptomethylthio)propane,5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

Aromatic polythiol: 1,2-dimercaptobenzene, 1,3-dimercaptobenzene,1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene,1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene,1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene,1,4-bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethoxy)benzene,1,3-bis(mercaptomethoxy)benzene, 1,4-bis(mercaptomethoxy)benzene,1,2-bis(mercaptoethoxy)benzene, 1,3-bis(mercaptoethoxy)benzene,1,4-bis(mercaptoethoxy)benzene, 1,2,3-trimercaptobenzene,1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene,1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene,1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene,1,2,3-tris(mercaptomethoxy)benzene, 1,2,4-tris(mercaptomethoxy)benzene,1,3,5-tris(mercaptomethoxy)benzene, 1,2,3-tris(mercaptoethoxy)benzene,1,2,4-tris(mercaptoethoxy)benzene, 1,3,5-tris(mercaptoethoxy)benzene,1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene,1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene,1,2,3,5-tetrakis(mercaptomethyl)benzene,1,2,4,5-tetrakis(mercaptomethyl)benzene,1,2,3,4-tetrakis(mercaptoethyl)benzene,1,2,3,5-tetrakis(mercaptoethyl)benzene,1,2,4,5-tetrakis(mercaptoethyl)benzene,1,2,3,4-tetrakis(mercaptoethyl)benzene,1,2,3,5-tetrakis(mercaptomethoxy)benzene,1,2,4,5-tetrakis(mercaptomethoxy)benzene,1,2,3,4-tetrakis(mercaptoethoxy)benzene,1,2,3,5-tetrakis(mercaptoethoxy)benzene,1,2,4,5-tetrakis(mercaptoethoxy)benzene, 2,2′-dimercaptobiphenyl,4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol,3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol,2,6-naphthalenedithiol, 2,7-naphthalenedithiol,2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1, 3-dithiol,9,10-anthracenedimethanethiol,1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol,2,4-di(p-mercaptophenyl)pentane and1,4-bis(mercaptopropylthiomethyl)benzene.

Halogen-substituted aromatic polythiol: 2,5-dichlorobenzene-1,3-dithiol,1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene.

Heterocycle-containing polythiol:2-methylamino-4,6-dithiol-sym-triazine,2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine,2-morpholino-4,6-dithiol-sym-triazine,2-cyclohexylamino-4,6-dithiol-sym-triazine,2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine,2-thiobenzeneoxy-4, 6-dithiol-sym-triazine,2-thiobutyloxy-4,6-dithiol-sym-triazine and1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

Sulfur atom-containing aromatic polythiol in addition to a mercaptogroup: 1,2-bis(mercaptomethylthio)benzene,1,3-bis(mercaptomethylthio)benzene, 1,4-bis(mercaptomethylthio)benzene,1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene,1,4-bis(mercaptoethylthio)benzene,1,2,3-tris(mercaptomethylthio)benzene,1,2,4-tris(mercaptomethylthio)benzene,1,3,5-tris(mercaptomethylthio)benzene,1,2,3-tris(mercaptoethylthio)benzene,1,2,4-tris(mercaptoethylthio)benzene,1,3,5-tris(mercaptoethylthio)benzene,1,2,3,4-tetrakis(mercaptomethylthio)benzene,1,2,3,5-tetrakis(mercaptomethylthio)benzene,1,2,4,5-tetrakis(mercaptomethylthio)benzene,1,2,3,4-tetrakis(mercaptoethylthio)benzene,1,2,3,5-tetrakis(mercaptoethylthio)benzene and1,2,4,5-tetrakis(mercaptoethylthio)benzene.

Sulfur atom-containing aliphatic polythiol in addition to a mercaptogroup: bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide,bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane,bis(2-mercaptoethylthio)methane, bis(3-mercaptopropyl)methane,1,2-bis(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane,1,2-(3-mercaptopropyl)ethane, 1,3-bis(mercaptomethylthio)propane,1,3-bis(2-mercaptoethylthio)propane,1,3-bis(3-mercaptopropylthio)propane,1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris(mercaptomethylthio)propane,1,2,3-tris(2-mercaptoethylthio)propane,1,2,3-tris(3-mercaptopropylthio)propane,tetrakis(mercaptomethylthiomethyl)methane,tetrakis(2-mercaptoethylthiomethyl)methane,tetrakis(3-mercaptopropylthiomethyl)methane,bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane,bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide,bis(mercaptopropyl)disulfide, an ester of thioglycolic acid ormercaptopropionic acid of the compound, hydroxymethylsulfidebis(2-mercaptoacetate), hydroxymethylsulfide bis(3-mercaptopropionate),hydroxyethylsulfide bis(2-mercaptoacetate), hydroxyethylsulfidebis(3-mercaptopropionate), hydroxypropylsulfide bis(2-mercaptoacetate),hydroxypropylsulfide bis(3-mercaptopropionate), hydroxymethyldisulfidebis(2-mercaptoacetate), hydroxymethyldisulfidebis(3-(mercaptopropionate), hydroxyethyldisulfidebis(2-mercaptoacetate), hydroxyethyldisulfide bis(3-mercaptopropionate),hydroxypropyldisulfide bis(2-mercaptoacetate), hydroxypropyldisulfidebis(3-mercaptopropionate), 2-mercaptoethylether bis(2-mercaptoacetate),2-mercaptoethylether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diolbis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate),2,5-bis(mercaptomethyl)-1,4-dithiane,2,5-bis(2-mercaptoethyl)-1,4-dithiane,2,5-bis(3-mercaptopropyl)-1,4-dithiane,2-(2-mercaptoethyl)-5-mercaptomethyl-1,4-dithiane,2-(2-mercaptoethyl)-5-(3-mercaptopropyl)-1,4-dithiane,2-mercaptomethyl-5-(3-mercaptopropyl)-1,4-dithiane, thioglycolic acidbis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethylester), 4,4′-thiodibutyl acid bis(2-mercaptoethyl ester),dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acidbis(2-mercaptoethyl ester), 4,4′-dithiodibutyl acid bis(2-mercaptoethylester), thiodiglycol acid bis(2,3-dimercaptopropyl ester),thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiglycolicacid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid(2,3-dimercaptopropyl ester),2-mercaptomethyl-6-mercapto-1,4-dithiacycloheptane,4,5-bis(mercaptomethylthio)-1,3-dithiolane,4,6-bis(mercaptomethylthio)-1,3-dithiane,2-bis(mercaptomethylthio)methyl-1,3-dithietane,2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane,1,2,7-trimercapto-4,6-dithiaheptane,1,2,9-trimercapto-4,6,8-trithianonan,1,2,11-trimercapto-4,6,8,10-tetrathiaundecane,1,2,13-trimercapto-4,6,8,10,12-pentathiatridecane,1,2,8,9-tetramercapto-4,6-dithianonane,1,2,10,11-tetramercapto-4,6,8-trithiaundecane,1,2,12,13-tetramercapto-4,6,8,10-tetrathiatridecane,bis(2,5-dimercapto-4-thiapentyl)disulfide,bis(2,7-dimercapto-4,6-dithiaheptyl)disulfide,1,2,5-trimercapto-4-thiapentane,3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane,3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane,3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane,3,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane,3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane,4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane,3-mercaptomethyl-1,6-dimercapto-2,5-dithiahexane,3-mercaptomethylthio-1,5-dimercapto-2-thiapentane,1,1,2,2-tetrakis(mercaptomethylthio)ethane,1,1,3,3-tetrakis(mercaptomethylthio)propane,1,4,8,11-tetramercapto-2,6,10-trithiaundecane,1,4,9,12-tetramercapto-2,6,7,11-tetrathiadodecane,2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia-1,7-heptanedithiol,2,3,5,6,8,9-hexathia-1,10-decanedithiol,2-(1-mercapto-2-mercaptomethyl-3-thiabutyl)-1,3-dithiolane,1,5-dimercapto-3-mercaptomethylthio-2,4-dithiapentane,2-mercaptomethyl-4-mercapto-1,3-dithiolane, 2,5-dimercapto-1,4-dithiane,2,6-dimercapto-1,4-dithiane, 2,4-dimercaptomethyl-1,3-dithietane,1,2,6,10,11-pentamercapto-4,8-dithiaundecane,1,2,9,10-tetramercapto-6-mercaptomethyl-4,7-dithiadecane,1,2,9,13,14-pentamercapto-6-mercaptomethyl-4,7,11-trithiatetradecane,1,2,6,10,14,15-hexamercapto-4,8,12-trithiapentadecane,1,4-dithiane-2,5-bis(4,5-dimercapto-2-thiapentane) and1,4-dithiane-2,5-bis(5,6-dimercapto-2,3-dithiahexane).

Sulfur atom-containing heterocycle-containing polythiol in addition to amercapto group: 3,4-thiophenedithiol,tetrahydrothiophene-2,5-dimercaptomethyl and2,5-dimercapto-1,3,4-thiadiazole.

Isocyanurate group-containing polythiol:1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate,1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trioneand tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate.

Moreover, as the (C-1) component in the present invention, a compoundhaving one or more hydroxyl groups and thiol groups each in one moleculecan also be used. Specific examples thereof can include the followingcompounds.

2-Mercaptoethanol, 3-mercapto-1,2-propanediol, glycerindi(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane,2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol,1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol,1,2-dimercapto-1,3-butanediol, pentaerythritoltris(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate),pentaerythritol bis(3-mercaptopropionate), pentaerythritoltris(thioglycolate), pentaerythritol pentakis(3-mercaptopropionate),hydroxymethyl-tris(mercaptoethylthiomethyl)methane,1-hydroxyethylthio-3-mercaptoethylthiobenzene,4-hydroxy-4′-mercaptodiphenylsulfone, 2-(2-mercaptoethylthio)ethanol,dihydroxyethylsulfide mono(3-mercaptopropionate), dimercaptoethanemono(salicylate) andhydroxyethylthiomethyl-tris(mercaptoethylthio)methane.

As the (C-1) component, a compound having a silsesquioxane structure canbe used in addition thereto. The silsesquioxane is a compoundrepresented by the following formula (5).

[Formula 14]

(R⁶—SiO_(3/2))_(n)   (5)

{where, a plurality of R⁶ are any of an organic group containing ahydroxyl group and/or thiol group, a hydrogen atom, an alkyl group, acycloalkyl group, an alkoxy group or a phenyl group, which may be thesame with or different from each other, and have two or more the organicgroup containing the hydroxyl group and/or thiol group in at least onemolecule, and a degree of polymerization n is an integer from 6 to100.}.

The organic group containing the hydroxyl group and/or thiol group in R⁶in the formula (5) is a monovalent hydrocarbon group having at least onehydroxyl group and/or thiol group bound thereto and having 1 to 10carbon atoms, or a monovalent group containing an oxygen atom or asulfur atom in a chain having at least one hydroxyl group and/or thiolgroup bound thereto and having 1 to 10 carbons. Specifically, preferredexamples include an alkylene chain having 1 to 10 carbon atoms, and anorganic group derived from polyol, polythiol or the like.

Moreover, the alkyl group in R⁶ is preferably an alkyl group having 1 to10 carbon atoms. Specific examples of the alkyl group having 1 to 10carbon atoms include a methyl group, an ethyl group, a n-propyl group,an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butylgroup, a n-pentyl group, a n-hexyl group, a n-octyl group and anisooctyl group.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 8carbon atoms. Specific examples of the cycloalkyl group having 3 to 8carbon atoms include a cyclopropyl group, a cyclobutyl group, acyclooctyl group, a cyclohexyl group, a cycloheptyl group and acyclooctyl group.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbonatoms. Specific examples of the alkoxy group having 1 to 6 carbon atomsinclude a methoxy group, an ethoxy group, a n-propoxy group, anisopropoxy group, a n-butoxy group, a sec-butoxy group and a tert-butoxygroup.

In general, a silsesquioxane compound can take various structures suchas a cage-like structure, a ladder-like structure and a randomstructure, but in the present invention, the silsesquioxane compound ispreferably a mixture formed of a plurality of structures.

<Preferred Examples of (C-1) Component>

Preferred examples of the poly(thi)ol compound being the (C-1) componentinclude: polyethylene polyol, polycaprolactone polyol, polycarbonatepolyol, trimethylolpropane, pentaerythritol, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), dipentaerythritolhexakis(3-mercaptopropionate), tetraethylene glycolbis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate),1,6-hexandiol bis(3-mercaptopropionate),1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,2,2-bis(mercaptomethyl)-1,4-butanedithiol,1,4-bis(mercaptopropylthiomethyl)benzene,2,5-bis(mercaptomethyl)-1,4-dithiane,4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,1,1,1,1-tetrakis(mercaptomethyl)methane,1,1,3,3-tetrakis(mercaptomethylthio)propane,1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-mercaptomethanol andtris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate.

Next, (C-2) mono(thi)ol compound having one hydroxyl group or one thiolgroup in one molecule will be described.

<(C-2) Mono(thi)ol Compound Having One Hydroxyl Group or One Thiol Groupin One Molecule>

In the present invention, the mono(thi)ol compound having one hydroxylgroup or one thiol group in one molecule (hereinafter, also referred tosimply as “mono(thi)ol compound”) can be used. If the opticalcomposition according to the present invention is cured, a rigid curedbody of a network structure having a (thio)urethane bond can be obtainedby a reaction of the polyiso(thio)cyanate compound with the poly(thi)olcompound. Further, a mono(thi)ol compound having one end-free structureis incorporated into the network structure by blending the (C-2)component into the optical composition, and therefore a flexible spaceis formed in the periphery of the mono(thi)ol compound. Accordingly, thereversible structural change of the photochromic compound existing inthe vicinity of the space is further immediately caused, and thereforethe photochromic cured body having excellent photochromiccharacteristics (the color optical density and the color fading rate)can be conceivably produced.

Further, the mono(thi)ol compound has only one hydroxyl group or onlyone thiol group, and therefore an amount of a hydrogen bond is smallerthan an amount in the poly(thi)ol compound. As a result, the mono(thi)olcompound has a high effect on reducing viscosity of the opticalcomposition.

Specific examples of the mono(thi)ol compound can include the compoundsdescribed below.

Compound having one hydroxyl group in one molecule: polyethylene glycolmonooleyl ether, polyoxyethylene oleate, polyethylene glycolmonolaurate, polyethylene glycol monostearate, polyethylene glycolmono-4-octylphenyl ether, straight-chain polyoxyethylene alkyl ether(polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether,polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether,polyoxyethylene cetyl ether, polyoxyethylene stearyl ether), andsaturated alkyl alcohol having a straight-chain or branched-chain shapeand having 5 to 30 carbon atoms.

Compound having one thiol group in one molecule: 3-methoxybutylthioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethyl octanoate,3-methoxybutyl 3-mercaptopropionate, 3-methoxybutyl thioglycolate, ethyl3-mercaptopropionate, 2-octyl 3-mercaptopropionate,n-octyl-3-mercaptopropionate, methyl-3-mercaptopropionate,tridecyl-3-mercaptopropionate, stearyl-3-mercaptopropionate andsaturated alkyl thiol having a straight-chain or branched-chainstructure and having 5 to 30 carbon atoms.

<Preferred Blending Proportion of (A), (B) and (C) Components>

Further, in the optical composition according to the present invention,with regard to an optimum blending proportion of the (A), (B) and (C)components described above for obtaining excellent moldability,mechanical strength and hardness in the optical article or excellentphotochromic characteristics upon adding the photochromic compoundthereto, to be described later, the resulting blend contains preferably(A) in the range from 3 to 15 parts by mass, (B) in the range from 25 to70 parts by mass, and (C) in the range from 20 to 65 parts by mass, andmost preferably (A) in the range from 4 to 10 parts by mass, (B) in therange from 30 to 60 parts by mass, and (C) in the range from 30 to 60parts by mass, when a total of the (A), (B) and (C) components describedabove is taken as 100 parts by mass.

<(D) Photochromic Compound>

The optical composition to which the photochromic compound is addedaccording to the present invention can be used as a photochromic opticalcomposition.

As the photochromic compound exhibiting the photochromism,publicly-known compounds per se can be used, and these compounds can beused alone, or in combination with two or more kinds thereof. Theplastic lens having the photochromic characteristics can be produced byadding these compounds to the optical composition and causingpolymerization curing of the resulting material.

Typified materials as such a photochromic compound include a fulgidecompound, a chromene compound and a spirooxazine compound, and aredisclosed in a lot of literature, such as JP-H2-28154 A, JP-S62-288830A, WO 94/22850 A and WO 96/14596 A, for example.

In the present invention, among the publicly-known photochromiccompounds, from a viewpoint of the photochromism such as color opticaldensity, initial coloring properties, durability and a color fadingrate, a chromene compound having an indeno[2,1-f]naphtho[1,2-b]pyranskeleton is further preferably used, and a chromene compound having amolecular weight of 540 or more is particularly preferably used becausethe compound is particularly excellent in the color optical density andthe color fading rate.

The chromene compounds shown below are examples of the chromenecompounds particularly preferably used in the present invention.

<Preferred Composition of the Photochromic Optical Composition>

In the optical composition according to the present invention, apreferred amount of use thereof is different also depending on a methodfor developing the photochromism. Upon polymerizing the composition intothe photochromic cured body by the kneading method, when thephotochromism of the photochromic cured body are developed, thephotochromic compound (D) is used preferably in an amount from 0.0001 to10 parts by mass, further preferably in an amount from 0.001 to 2 partsby mass, and most preferably in an amount from 0.001 to 1 part by mass,based on a total of 100 parts by mass of the (A) component, the (B)component and the (C) component. Moreover, when the photochromism isdeveloped by the lamination method, the photochromic compound (D) isused preferably in an amount from 0.01 to 20 parts by mass, and furtherpreferably in an amount from 0.01 to 10 parts by mass. Moreover, whenthe photochromism is developed by the binder method, the component (D)is used preferably in an amount from 0.1 to 40 parts by mass, andfurther preferably from 0.5 to 20 parts by mass.

<(E) Resin Modifier, (F) Polymerization Curing Accelerator or (G)Internal Mold Release Agent>

In the optical composition according to the present invention, inaddition to each component of (A), (B) and (C), the optical compositionmay further contain a resin modifier (E), a polymerization curingaccelerator (F) or an internal mold release agent (G) for the purpose ofimproving a refractive index, moldability, adjusting hardness of thecured body and the like. These materials will be described.

<(E) Resin Modifier>

In the present invention, the resin modifier can be added thereto forthe purpose of improving the refractive index of the cured body to beobtained, or adjusting the hardness thereof. Specific examples includean episulfide-based compound, a thietanyl-based compound, an epoxycompound and an olefin compound containing a (meth)acrylate compound.Specific examples will be described below.

<Episulfide-Based Compound>

The episulfide-based compound is a compound having two or moreepisulfide groups in one molecule, and is cured by the ring-openingpolymerization. These compounds may be added thereto for achieving ahigh refractive index. Specific examples of such an episulfide compoundcan include compounds described below.

Bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide,bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropylthio)methane,bis(2,3-epithiopropyl)disulfide, bis(2,3-epithiopropyldithio)methane,bis(2,3-epithiopropyldithio)ethane,bis(6,7-epithio-3,4-dithiaheptyl)sulfide,bis(6,7-epithio-3,4-dithiaheptyl)disulfide,1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl),1,3-bis(2,3-epithiopropyldithiomethyl)benzene,1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane,1,2,3-tris(2,3-epithiopropyldithio)propane,1,1,1,1-tetrakis(2,3-epithiopropyldithiomethyl)methane,1,3-bis(2,3-epithiopropyldithio)-2-thiapropane,1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane,1,1,1-tris(2,3-epithiopropyldithio)methane,1,1,1-tris(2,3-epithiopropyldithiomethylthio)methane,1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane,1,1,2,2-tetrakis(2,3-epithiopropyldithiomethylthio)ethane,1,1,3,3-tetrakis(2,3-epithiopropyldithio)propane,1,1,3,3-tetrakis(2,3-epithiopropyldithiomethylthio)propane,2-[1,1-bis(2,3-epithiopropyldithio)methyl]-1,3-dithietane and2-[1,1-bis(2,3-epithiopropyldithiomethylthio)methyl]-1,3-dithietane.

<Thietanyl-Based Compound>

The thietanyl-based compound is a thietane compound having two or morethietanyl groups in one molecule, and is cured by the ring-openingpolymerization. These compounds may be added thereto for achieving thehigh refractive index. A part of such a thietanyl compound has anepisulfide group together with a plurality of thietanyl groups, whichare listed in the section of the episulfide-based compound describedabove. Other thietanyl compounds include a metal-containing thietanecompound having a metal atom in the molecule, and a non-metal thietanecompound containing no metal therein. Specific examples of such athietanyl compound can include the compounds described below.

Non-metal thietane compound: bis(3-thietanyl)disulfide,bis(3-thietanyl)sulfide, bis(3-thietanyl)trisulfide,bis(3-thietanyl)tetrasulfide, 1,4-bis(3-thietanyl)-1,3,4-trithiabutane,1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane,1,6-bis(3-thietanyl)-1,3,4,6-tetrathiahexane,1,6-bis(3-thietanyl)-1,3,5,6-tetrathiahexane,1,7-bis(3-thietanyl)-1,2,4,5,7-pentathiaheptane,1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathiaheptane,1,1-bis(3-thietanylthio)methane, 1,2-bis(3-thietanylthio)ethane,1,2,3-tris(3-thietanylthio)propane,1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane, 1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane,2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, bisthietanylsulfide, bis(thietanylthio)methane,3-[<(thietanylthio)methylthio>methylthio]thiethane, bisthietanyldisulfide, bisthietanyl trisulfide, bisthietanyl tetrasulfide,bisthietanyl pentasulfide, 1,4-bis(3-thietanyldithio)-2,3-dithiabutane,1,1,1-tris(3-thietanyldithio)methane,1,1,1-tris(3-thietanyldithiomethylthio)methane,1,1,2,2-tetrakis(3-thietanyldithio)ethane and1,1,2,2-tetrakis(3-thietanyldithiomethylthio)ethane.

<Metal-Containing Thietane Compound>

This thietane compound contains a Group 14 element such as a Sn atom, aSi atom, a Ge atom and a Pb atom; a Group 4 element such as a Zr atomand a Ti atom; a Group 13 element such as an Al atom; or a Group 12element such as a Zn atom, as a metal atom in the molecule. For example,the compounds described below are particularly preferably used.

Alkylthio(thietanylthio)tin: methylthio tris(thietanylthio)tin,ethylthio tris(thietanylthio)tin, propylthio tris(thietanylthio)tin andisopropylthio tris(thietanylthio)tin.

Bis(alkylthio)bis(thietanylthio)tin:bis(methylthio)bis(thietanylthio)tin, bis (ethylthio) bis(thietanylthio) tin, bis(propylthio)bis(thietanylthio)tin andbis(isopropylthio)bis(thietanylthio)tin.

Alkylthio(alkylthio)bis(thietanylthio)tin:ethylthio(methylthio)bis(thietanylthio)tin,methylthio(propylthio)bis(thietanylthio)tin,isopropylthio(methylthio)bis(thietanylthio)tin,ethylthio(propylthio)bis(thietanylthio)tin,ethylthio(isopropylthio)bis(thietanylthio)tin andisopropylthio(propylthio)bis(thietanylthio)tin.

Bis(thietanylthio)cyclic dithiotin compound:bis(thietanylthio)dithiastannetane, bis(thietanylthio)dithiastannolane,bis(thietanylthio)dithiastanninane andbis(thietanylthio)trithiastannokane.

Alkyl(thietanylthio)tin compound: methyl tris(thietanylthio)tin,dimethyl bis(thietanylthio)tin, butyl tris(thietanylthio)tin,tetrakis(thietanylthio)tin, tetrakis(thietanylthio)germanium andtris(thietanylthio)bismuth.

<Epoxy Compound>

The epoxy compound has an epoxy group as a polymerizable group in themolecule, and is cured by the ring-opening polymerization. Thesecompounds may be added thereto for adjusting the refractive index andthe hardness of the lens. Such an epoxy compound is generally classifiedinto an aliphatic epoxy compound, an alicyclic epoxy compound and anaromatic epoxy compound, and specific examples thereof can include thecompounds described below.

Aliphatic epoxy compound: ethylene oxide, 2-ethyl oxirane, butylglycidyl ether, phenyl glycidyl ether, 2,2′-methylene bis oxirane,1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether,diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether,tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidylether, propylene glycol diglycidyl ether, dipropylene glycol diglycidylether, tripropylene glycol diglycidyl ether, tetrapropylene glycoldiglycidyl ether, nonapropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, trimethylolpropane triglycidyl ether, glyceroltriglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritoltetraglycidyl ether, diglycidyl ether oftris(2-hydroxyethyl)isocyanurate and triglycidyl ether oftris(2-hydroxyethyl)isocyanurate.

Alicyclic epoxy compound: isophoronediol diglycidyl ether andbis-2,2-hydroxycyclohexylpropane diglycidyl ether.

Aromatic epoxy compound: resorcin diglycidyl ether, bisphenol Adiglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidylether, o-phthalic acid diglycidyl ester, phenol novolak polyglycidylether and cresol novolak polyglycidyl ether.

Moreover, in addition to the compounds described above, an epoxycompound having a sulfur atom together with an epoxy group in themolecule can also be used. Such a sulfur atom-containing epoxy compoundparticularly contributes to improvement in the refractive index, andincludes a chain aliphatic group-based compound and a cyclic aliphaticgroup-based compound. Specific examples thereof are as described below.

Chain aliphatic group-based sulfur atom-containing epoxy compound:bis(2,3-epoxypropyl)sulfide, bis(2,3-epoxypropyl)disulfide,bis(2,3-epoxypropylthio)methane, 1,2-bis(2,3-epoxypropylthio)ethane,1,2-bis(2,3-epoxypropylthio)propane,1,3-bis(2,3-epoxypropylthio)propane,1,3-bis(2,3-epoxypropylthio)-2-methylpropane,1,4-bis(2,3-epoxypropylthio)butane,1,4-bis(2,3-epoxypropylthio)-2-methylbutane,1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio)pentane,1,5-bis(2,3-epoxypropylthio)-2-methylpentane,1,5-bis(2,3-epoxypropylthio)-3-thiapentane,1,6-bis(2,3-epoxypropylthio)hexane,1,6-bis(2,3-epoxypropylthio)-2-methylhexane,3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane,1,2,3-tris(2,3-epoxypropylthio)propane,2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propaneand 2,2-bis(2,3-epoxypropylthiomethyl)-1-(2,3-epoxypropylthio)butane.

Cyclic aliphatic group-based sulfur atom-containing epoxy compound:1,3-bis(2,3-epoxypropylthio)cyclohexane, 1,4-bis(2,3-epoxypropylthio)cyclohexane, 1,3-bis(2,3-epoxypropylthiomethyl)cyclohexane,1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane,2,5-bis(2,3-epoxypropylthiomethyl)-1,4-dithiane,2,5-bis[<2-(2,3-epoxypropylthio)ethyl>thiomethyl]-1,4-dithiane and2,5-bis(2,3-epoxy-propylthiomethyl)-2,5-dimethyl-1,4-dithiane.

<Olefin Compound Containing a (meth)Acrylate Compound, and CompoundsHaving Other Radical Polymerizable Groups>

An olefin compound containing a (meth)acrylate compound and compoundshaving other radical polymerizable groups each have a radicalpolymerizable group as a polymerizable group in the molecule, and arecured by the radical polymerization. These compounds can be used foradjusting the hardness of the lens, and specific examples thereof caninclude compound described below.

(Meth)acrylate compound: ethylene glycol diacrylate, ethylene glycoldimethacrylate, diethylene glycol diacrylate, diethylene glycoldimethacrylate, triethylene glycol diacrylate, triethylene glycoldimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, polyethylene glycol diacrylate, polyethylene glycoldimethacrylate, propylene glycol diacrylate, propylene glycoldimethacrylate, dipropylene glycol diacrylate, dipropylene glycoldimethacrylate, tripropylene glycol diacrylate, tripropylene glycoldimethacrylate, polypropylene glycol dimethacrylate, polypropyleneglycol diacrylate, neopentyl glycol diacrylate, neopenthyl glycoldimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycolbisglycidyl methacrylate, bisphenol A diacrylate, bisphenol Adimethacrylate, 2,2-bis(4-acryloxyethoxyphenyl)propane,2,2-bis(4-methacryloxyethoxyphenyl)propane,2,2-bis(4-acryloxydiethoxyphenyl)propane,2,2-bis(4-methacryloxydiethoxyphenyl)propane,2,2-bis(4-methacryloyloxyethoxyphenyl)propane,2,2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane,2,2-bis(4-methacryloyloxydipropoxyphenyl)propane, bisphenol Fdiacrylate, bisphenol F dimethacrylate,1,1-bis(4-acryloxyethoxyphenyl)methane,1,1-bis(4-methacryloxyethoxyphenyl)methane,1,1-bis(4-acryloxydiethoxyphenyl)methane,1,1-bis(4-methacryloxydiethoxyphenyl)methane, dimethyloltricyclodecanediacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, ditrimethylolpropane tetraacrylate,ditrimethylolpropane tetramethacrylate, glycerol diacrylate, glyceroldimethacrylate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, pentaerythritol tetramethacrylate, methylthio acrylate,methylthio methacrylate, phenylthio acrylate, benzylthio methacrylate,xylylenedithiol diacrylate, xylylenedithiol dimethacrylate,mercaptoethylsulfide diacrylate, mercaptoethylsulfide dimethacrylate,bifuntional urethane acrylate and bifunctional urethane methacrylate.

Allyl compound: allyl glycidyl ether, diallyl phthalate, diallylterephthalate, diallyl isophthalate, diallyl carbonate, diethyleneglycol bis allyl carbonate and methoxy polyethylene glycol allyl ether.

Vinyl compound: a-methylstyrene, an a-methylstyrene dimer, styrene,chlorostyrene, methylstyrene, bromostyrene, dibromostyrene,divinylbenzene and 3,9-divinyl spirobi(m-dioxane).

<(F) Polymerization Curing Accelerator>

In the optical composition according to the present invention, variouspolymerization curing accelerators can be used for immediatelyaccelerating the polymerization curing according to a kind of thecompound described above.

For example, when the accelerator is used for a reaction of the hydroxylgroup and the thiol group with a NCO group and a NCS group, a reactioncatalyst for urethane or urea or a condensation agent is used as thepolymerization curing accelerator.

When the episulfide-based compound, the thietanyl-based compound or theepoxy compound is used therefor, a cationic polymerization catalyst forallowing the ring-opening polymerization of an epoxy curing agent or theepoxy group is used as the polymerization curing accelerator.

When the composition contains a compound having a (meth)acryl group, andother radical polymerizable groups (the olefin compound containing the(meth)acrylate compound and the compounds having other radicalpolymerizable groups), a radical polymerization initiator is used as thepolymerization curing accelerator.

<Reaction Catalyst for Urethane or Urea>

This reaction catalyst is used in formation of a poly(thio)urethane bondby a reaction of polyiso(thia)cyanate with polyol or polythiol. Specificexamples of these polymerization catalysts include tertiary amines andinorganic or organic salts corresponding thereto, phosphines, quaternaryammonium salts, quaternary phosphonium salts, Lewis acids or organicsulfonic acid.

Specific examples thereof can include the compounds described below.Moreover, when catalyst activity is excessively high depending on a kindof the compound to be selected as described above, the catalyst activitycan be suppressed by mixing tertiary amine and Lewis acid and using theresulting mixture.

Tertiary amines: triethylamine, tri-n-propylamine, triisopropylamine,tri-n-butylamine, triisobutylamine, triethylamine,hexamethylenetetramine, N,N-dimethyloctylamine,N,N,N′,N′-tetramethyl-1,6-diaminohexane, 4,4′-trimethylenebis(1-methylpiperidine) and 1,8-diazabicyclo-(5,4,0)-7-undecene.

Phosphines: trimethylphosphine, triethylphosphine,tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,triphenylphosphine, tribenzylphosphine, 1,2-bis(diphenylphosphino)ethaneand 1,2-bis(dimethylphosphino)ethane.

Quaternary ammonium salts: tetramethylammonium bromide,tetrabutylammonium chloride and tetrabutylammonium bromide.

Quaternary phosphonium salts: tetramethylphosphonium bromide,tetrabutylphosphonium chloride and tetrabutylphosphonium bromide.

Lewis acid: triphenyl aluminum, dimethyltin dichloride, dimethyltinbis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate,dibutyltin maleate, a dibutyltin maleate polymer, dibutyltindiricinolate, dibutyltin bis(dodecylmercaptide), dibutyltinbis(isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, adioctyltin maleate polymer, dioctyltin bis(butylmaleate), dioctyltindilaurate, dioctyltin diricinolate, dioctyltin dioleate, dioctyltindi(6-hydroxy) caproate, dioctyltin bis(isooctylthioglycolate),didodecyltin diricinolate; and various metal salts such as copperoleate, copper acetylacetonate, iron acetylacetonate, iron naphthenate,iron lactate, iron citrate, iron gluconate, potassium octoate and2-ethylhexyl titanate.

Organic sulfonic acid: methanesulfonic acid, benzenesulfonic acid andp-toluenesulfonic acid.

<Condensation Agent>

Specific examples of the condensation agent can include the compoundsdescribed below.

Inorganic acid: hydrogen chloride, hydrogen bromide, sulfuric acid andphosphoric acid.

Organic acid: p-toluenesulfonic acid and camphorsulfonic acid.

Acidic ion-exchange resin: Amberlite and Amberlyst.

Carbodiimide: dicyclohexylcarbodiimide and1-ethyl-3-(3-dimethylaminopyrrolyl)-carbodiimide.

<Epoxy Curing Agent>

Specific examples of the epoxy curing agent can include the compoundsdescribed below.

Amine compound and salt thereof: 2-methylimidazole,2-ethyl-4-methylimidazole,1,8-diaza-bicyclo(5,4,0)undecene-7-trimethylamine, benzyldimethylamine,triethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and2-(dimethylaminomethyl) phenol.

Quaternary ammonium salt: tetramethylammonium chloride,benzyltrimethylammonium bromide and tetrabutylammonium bromide.

Organic phosphine compound: tetra-n-butylphosphonium benzotriazolate andtetra-n-butylphosphonium-o,o-diethyl phosphorodithioate.

Metal carboxylate: chromium(III) tricarboxylate and tin octylate.

Acetylacetone chelate compound: chromium acetylacetonate.

<Cationic Polymerization Catalyst>

Specific examples of the cationic polymerization catalyst can includethe compounds described below.

Lewis acid-based catalyst: a BF₃-amine complex, PF₅, BF₃, AsF₅ and SbF₅.

Thermosetting cationic polymerization catalyst: a phosphonium salt or aquaternary ammonium salt, a sulfonium salt, a benzylammonium salt, abenzylpyridinium salt, a benzylsulfonium salt, a hydrazinium salt,carboxylate, sulfonate and amineimide.

Ultraviolet curable cationic polymerization catalyst: diaryliodoniumhexafluorophosphate and bis(dodecylphenyl)iodonium hexafluoroantimonate.

<Radical Polymerization Initiator>

The polymerization initiator includes a thermal polymerizationinitiator, and specific examples are as described below.

Diacyl peroxide: benzoyl peroxide, p-chlorobenzoyl peroxide, decanoylperoxide and lauroyl peroxide.

Acetyl peroxide peroxyester: t-butylperoxy-2-ethyl hexanate,t-butylperoxy neodecanoate, cumylperoxy neodecanoate and t butylperoxybenzoate.

Percarbonate: diisopropyl peroxydicarbonate and di-sec-butylperoxydicarbonate.

Azo compound: azobisisobutyronitrile.

The various polymerization curing accelerators (E) described above eachcan be used alone or in combination with two or more kinds, and anamount of use thereof may be a so-called “catalyst amount”. For example,the amount may be as small as in the range from 0.001 to 10 parts bymass, and particularly from 0.01 to 5 parts by mass, based on a total of100 parts by mass of the (A), (B) and (C) described above.

<(G) Internal Mold Release Agent>

As an example of the internal mold release agent used in the presentinvention, any agent can be used, as long as the agent has an effect ofreleasability and does not adversely affect physical properties of theresin, such as transparency, and a surfactant is preferably used. Aboveall, a phosphate-based surfactant is preferable. The internal moldrelease agent herein also includes an agent that exhibits a releasingeffect among the various catalysts described above, and includes, forexample, quaternary ammonium salts and quaternary phosphonium salts inseveral cases. These internal mold release agents are appropriatelyselected depending on a combination with a monomer, polymerizationconditions, economic efficiency, and ease of handling. Specific examplesof the internal mold release agent of the phosphate are as describedbelow.

Alkyl acid phosphate: mono-n-butyl phosphate, mono-2-ethylhexylphosphate, mono-n-octyl phosphate, mono-n-butyl phosphate,bis(2-ethylhexyl)phosphate, di(2-ethylhexyl)phosphate, di-n-octylphosphate, di-n-butyl phosphate, butyl acid phosphate (mono- and di-mixture), ethyl acid phosphate (mono- and di-mixture), butoxyethyl acidphosphate (mono- and di- mixture), 2-ethylhexyl acid phosphate (mono-and di-mixture), isotridecyl acid phosphate (mono- and di-mixture),tetracosyl acid phosphate (mono- and di-mixture) and stearyl acidphosphate (mono- and di-mixture).

Other phosphates: oleyl acid phosphate (mono- and di-mixture), dibutylpyrophosphate, ethylene glycol acid phosphate (mono- and di-mixture) andbutoxyethyl acid phosphate (mono- and di-mixture).

The various internal mold release agents (G) described above each can beused alone or in combination with two or more kinds, and an amount ofuse thereof may be small. For example, the internal mold release agentcan be used in an amount from 0.001 to 10 parts by mass based on a totalof 100 parts by mass of (A), (B) and (C).

<Other Blending Components>

Upon adding the photochromic compound to the optical compositionaccording to the present invention, publicly-known various blendingagents per se can be blended, when necessary, within the range in whichadvantageous effects of the present invention are not adverselyaffected. For example, various stabilizers such as an ultravioletabsorber, an antistatic agent, an infrared absorber, an ultravioletstabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, afluorescent dye, a dye, a pigment and a flavoring agent, and anadditive, a solvent, a leveling agent, and further thiols such ast-dodecylmercaptan as a polymerization modifier can be added thereto.

Above all, if the ultraviolet stabilizer is used therefor, durability ofthe photochromic compound can be improved, and therefore such use ispreferable. As such an ultraviolet stabilizer, a hindered amine lightstabilizer, a hindered phenol antioxidant, a sulfur-type antioxidant orthe like is known. Particularly preferred ultraviolet stabilizers are asdescribed below.

Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, ADK STAB LA-52, LA-57,LA-62, LA-63, LA-67, LA-77, LA-82 and LA-87, manufactured by ADEKACorporation, 2,6-di-t-butyl-4-methyl-phenol, ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], andIRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259,3114, 3790, 5057 and 565, manufactured by Ciba Specialty Chemicals Co.,Ltd.

An amount of use of such an ultraviolet stabilizer is not particularlylimited, as long as the advantageous effects of the present inventionare not adversely affected, but the amount is ordinarily in the rangefrom 0.001 part by mass to 10 parts by mass, and particularly in therange from 0.01 part by mass to 1 part by mass, based on a total of 100parts by mass of (A), (B) and (C). In particular, when the hinderedamine light stabilizer is used, an effect of improving the durability isdifferent depending on a kind of the photochromic compound. As a result,in order to avoid occurrence of color shift of an adjusted coloringtone, the amount should be adjusted to an amount from 0.5 to 30 mol,further preferably from 1 to 20 mol, and still further preferably from 2to 15 mol per one mol of the photochromic compound (D).

Moreover, specific examples of the antistatic agent include an alkalimetal or alkaline earth metal salt, a quaternary ammonium salt, asurfactant (a nonionic surfactant, an anionic surfactant, a cationicsurfactant, and an amphoteric surfactant), and an ionic liquid (a saltexisting in the form of liquid at ordinary temperature and existing in apair of a cation and an anion). Specific examples thereof are asdescribed below.

Alkali metal or alkaline earth metal salt: a salt between alkali metal(lithium, sodium and potassium) or alkaline earth metal (magnesium andcalcium) and organic acid [monocarboxylic acid or dicarboxylic acidhaving 1 to 7 carbon atoms (formic acid, acetic acid, propionic acid,oxalic acid and succinic acid), sulfonic acid having 1 to 7 carbon atoms(methanesulfonic acid, trifluoromethanesulfonic acid andp-toluenesulfonic acid), and thiocyanic acid]; and a salt between theorganic acid and inorganic acid [halogenated hydroacid (hydrochloricacid and hydrobromic acid), perchloric acid, sulfuric acid, nitric acidand phosphoric acid].

Quaternary ammonium salt: a salt between amidinium(1-ethyl-3-methylimidazolium) or guanidinium(2-dimethylamino-1,3,4-trimethylimidazolium) and the organic acid orinorganic acid.

Surfactant: sucrose fatty acid ester, sorbitan fatty acid ester,polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acidester, fatty acid alkanolamide, polyoxyethylene alkyl ether, alkylglycoside, polyoxyethylene alkylphenyl ether, a higher fatty acid salt(soap), an α-sulfo fatty acid methyl ester salt, straight-chainalkylbenzene sulfonate, alkyl sulfate, alkylether sulfate, (mono)alkylphosphate, α-olefin sulfonate, alkane sulfonate, analkyltrimethylammonium salt, a dialkyldimethylammonium salt, analkyldimethylbenzylammonium salt, N-methyl-bis-hydroxyethylamine fattyacid ester-hydrochloride, an alkylamino fatty acid salt, alkyl betaineand alkylamineoxide.

Ionic liquid: 1,3-ethylmethylimidazolium bistrifluoromethanesulfonimide,1,3-ethylmethylimidazorium tetrafluoroborate, 1-ethylpyridiniumbistrifluoromethanesulfonimide, 1-ethylpyridinium tetrafluoroborate,1-ethylpyridinium hexafluorophosphate and 1-methylpyrazoliumbistrifluoromethanesulfonimide.

Further, in the present invention, in order to develop a maximum of theeffect of improving the photochromism, with regard to a functional groupmole ratio of the hydroxyl group and the thiol group to the isocyanategroup and the thioisocyanate group, an amount of the hydroxyl group andthe thiol group per one mol of the isocyanate group and thethioisocyanate group should be adjusted to the range from 0.8 to 1.2mol, particularly preferably from 0.85 to 1.15 mol, and most preferablyfrom 0.9 to 1.1 mol.

<Production Method for a Photochromic Optical Composition>

When the optical composition according to the present invention is usedas the photochromic optical composition, in general, in addition to (A)the polyrotaxane, (B) the compound having two or more groups of at leastone kind of group selected from the isocyanate group and theisothiocyanate group in one molecule, and (D) the photochromic compound,(C) the iso(thio)cyanate reactive group-containing compound ispreferably blended therein. For example, the photochromism is desirablydeveloped by preparing the photochromic optical composition by meltingand kneading each component, preparing the photochromic cured body byallowing polymerization curing of the resulting material, and by usingthe cured body.

Moreover, when the optical composition according to the presentinvention is used as a photochromic coating agent for improvingsolubility of a constituent or adjusting a film thickness, aphotochromic coating layer is formed by preparing a coating liquid bydispersing or dissolving the photochromic optical composition into anorganic solvent, and coating the resulting coating liquid onto atransparent optical sheet or optical film and drying the resultingmaterial, thereby enabling to develop the photochromism. The organicsolvent to be used only needs to be selected appropriately according touse thereof, but in view of the solubility, ketones such as methyl ethylketone and diethyl ketone, halogens such as methylene chloride andchloroform, aromatic hydrocarbons such as toluene and xylene, and etherssuch as dioxane and tetrahydropyan are preferably used.

In the photochromic optical composition, the polymerization curing isperformed in order to prepare the photochromic cured body. Thepolymerization curing is performed by performing the radicalpolymerization, the ring-opening polymerization, the anionicpolymerization or polycondensation by using heat, or when necessary,irradiation with active energy rays such as ultraviolet rays, α-rays,β-rays and γ-rays or heat, or simultaneous use of both of heat andirradiation, or the like. More specifically, an appropriatepolymerization means only needs to be adopted according to a kind of (A)the polyrotaxane, (C) the iso(thio)cyanate reactive group-containingcompound, (E) the resin modifier, and further (D) the polymerizationcuring accelerator, and a form of the photochromic curing body to beformed.

Upon allowing thermal polymerization of the photochromic opticalcomposition, a temperature during the polymerization particularlyinfluences properties of the photochromic cured body to be obtained. Thetemperature conditions are influenced by a kind and an amount of thethermal polymerization initiator or a kind of the polymerizable monomer,and therefore are unable to be unequivocally limited. However, ingeneral, a method in which the polymerization is started at a relativelylow temperature, and the temperature is gradually increased ispreferable. A polymerization time is also different depending on variousfactors in a manner similar to the temperature. Therefore, an optimumtime according to these conditions is preferably determined in advance.However, in general, the conditions are preferably selected in such amanner that the polymerization is completed in 2 to 48 hours. When aphotochromic laminate sheet is obtained, the polymerization ispreferably performed at a temperature at which a reaction between thepolymerization functional groups progresses, and on the above occasion,an optimum temperature and the optimum time are preferably determined soas to achieve an objective molecular weight.

Moreover, upon allowing photopolymerization of the photochromic opticalcomposition, among the polymerization conditions, ultraviolet intensityparticularly influences the properties of the photochromic cured body tobe obtained. The illuminance conditions are influenced by a kind and anamount of the photopolymerization initiator and a king of thepolymerizable monomer, and therefore are unable to be unequivocallylimited. However, in general, the conditions are preferably selected soas to irradiate the composition with ultraviolet rays having awavelength of 365 nm and 50 to 500 mW/cm² for 0.5 to 5 minutes.

When the photochromism is developed by the kneading method by using thepolymerization curing described above, the photochromic cured bodyshaped into the form of the optical material such as the lens can beobtained by casting the photochromic optical composition into a spacebetween the glass molds kept by an elastomer gasket or spacer, and byperforming cast polymerization by heating the composition in an air ovenor irradiating the composition with the active energy rays such as theultraviolet rays according to a kind of the polymerizable monomer or thepolymerization curing agent. According to such a method, an eyeglasslens provided with the photochromism or the like is directly obtained.

When the photochromism is developed by the lamination method, thecoating liquid of the photochromic optical composition is coated onto asurface of the optical base material such as a lens base material byspin coating, dipping or the like. When the photochromic opticalcomposition has high viscosity, the photochromic optical compositiononly needs to be appropriately dissolved into the organic solvent toprepare the coating liquid, and the coating liquid may be coatedthereonto, and dried to remove the organic solvent. A photochromic layerformed of the photochromic cured body is formed on the surface of theoptical base material by subsequently performing thermosetting byheating the composition (coating method). Moreover, upon using amaterial having a radical polymerizable group in the resin modifier, thepolymerization curing may be performed by irradiation with ultravioletrays, heating or the like in an inert gas such as nitrogen.

Moreover, the photochromic layer formed of the photochromic cured bodycan be formed on the surface of the optical base material also by castpolymerization by inner molding, in which an optical substrate such asthe lens base material is arranged by being faced with the glass mold sothat a predetermined airspace is formed therebetween, the photochromicoptical composition is cast into this airspace, and the polymerizationcuring is performed by irradiation with ultraviolet rays, heating or thelike in this state.

When the photochromic layer is formed on the surface of the optical basematerial by the lamination method (the coating method and the castpolymerization method) as described above, adhesion between thephotochromic layer and the optical base material can also be improved byapplying, onto the surface of the optical base material in advance,chemical treatment by an alkali solution, an acid solution or the like,or physical treatment by corona discharge, plasma discharge, polishingor the like. A transparent adhesive resin layer can also be obviouslyprovided on the surface of the optical base material.

Further, when the photochromism is developed by the binder method, thephotochromic laminate in which the photochromic layer is applied as anadhesive layer is obtained by preparing a photochromic sheet by sheetforming using the photochromic optical composition, interposing theresulting sheet by two transparent sheets (optical sheets) andperforming the polymerization curing described above.

In this case, in preparing the photochromic sheet, a means of coatingusing the coating liquid in which the photochromic optical compositionis dissolved into the organic solvent can also be employed.

The thus prepared photochromic laminate is placed within a mold, forexample, and then a thermoplastic resin (for example, polycarbonate) forthe optical base material such as the lens is injection-moldedthereonto. Thus, the optical base material such as the lens having apredetermined shape and provided with the photochromism is obtained.Moreover, this photochromic laminate can be adhered onto the surface ofthe optical base material by an adhesive or the like. Thus, thephotochromic lens can also be obtained.

The photochromic optical composition described above can causedevelopment of the photochromism excellent in the color optical density,the color fading rate or the like, and furthermore can be effectivelyused for preparing the optical base material provided with thephotochromism, for example, the photochromic lens, without reducing thecharacteristics such as the mechanical strength.

Moreover, onto the photochromic layer or the photochromic cured bodyformed using the photochromic optical composition, post-treatment can beapplied, according to use thereof, such as dyeing using a dye such as adisperse dye, preparation of a hard coat film using a silane couplingagent or a hard coat agent containing as a main component a sol ofsilicon, zirconium, antimony, aluminum, tin and tungsten, formation of athin film by vapor deposition of metallic oxide such as SiO₂, TiO₂ andZro₂, and anti-reflection treatment and antistatic treatment by a thinfilm by applying an organic polymer thereonto.

EXAMPLES

Next, the present invention will be described in detail using Examplesand Comparative Examples, but the present invention is not limited tothe present Examples. In the Examples and Comparative Examples describedbelow, evaluation methods for each component and photochromiccharacteristics above are as described below.

(A) Preparation of a Polyrotaxane being Characterized in that a SideChain Having a Secondary or Tertiary Hydroxyl Group is Introduced intoat Least Part of a Cyclic Molecule (Polyrotaxane According to Aspect I)

AI-1: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

Hereinafter, a preparation method for a polyrotaxane (AI-1) will bedescribed below.

(1-1) Preparation of PEG-COOH:

As a polymer for forming an axle molecule, straight-chain polyethyleneglycol (PEG) having a weight average molecular weight of 20,000 wasarranged.

Each component was dissolved into 100 mL of water according to theformulation described below:

10 g of PEG

100 mg of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) 1 g ofsodium bromide

To this solution, 5 mL of commercially available sodium hypochloriteaqueous solution (available chlorine concentration: 5%) was added, andthe resulting mixture was stirred at room temperature for 10 minutes.Then, ethanol was added thereto in the range of a maximum of up to 5 mLto terminate the reaction. Then, extraction using 50 mL of methylenechloride was performed, and then methylene chloride was distilled off,the resulting material was dissolved into 250 mL of ethanol, and thencaused reprecipitation in 12 hours at a temperature of −4° C., andPEG-COOH was collected and dried.

(1-2) Preparation of a Polyrotaxane Having a Primary Hydroxyl Group in aSide Chain

Into 50 mL of warm water at 70° C., 3 g of PEG-COOH prepared asdescribed above and 12 g of α-cyclodextrin (α-CD) were each dissolved,and the resulting each solution was mixed and shaken up well.Subsequently, reprecipitation was caused in this mixed solution at atemperature of 4° C. for 12 hours, and a precipitated clathrate complexwas freeze-dried and collected. Then, 0.13 g of adamantanamine wasdissolved into 50 mL of dimethylformamide (DMF) at room temperature, andthen the clathrate complex described above was added thereto, and theresulting mixture was immediately shaken up well. Subsequently, asolution in which 0.38 g of BOP reagent(benzotriazol-1-yl-oxy-tris(dimethylamino)phosphoniumhexafluorophosphate) was dissolved into DMF was further added thereto,and the resulting mixture was shaken up well. Further, a solution inwhich 0.14 mL of diisopropylethylamine was dissolved into DMF was addedthereto, and the resulting mixture was shaken up well to obtain aslurry-form reagent. The slurry-form reagent obtained as described abovewas left to stand at 4° C. for 12 hours. Then, 50 mL of DMF/methanolmixed solvent (volume ratio: 1/1) was added thereto, and mixed, and theresulting mixture was centrifuged, and a supernatant was disposed of.Further, the resulting material was washed with the DMF/methanol mixedsolution, and then washed using methanol, and centrifuged to obtain adeposit. The deposit obtained was dried in vacuum, and then dissolvedinto 50 mL of DMSO (dimethylsulfoxide), and a transparent solutionobtained was added dropwise into 700 mL of water to precipitate apolyrotaxane. The polyrotaxane precipitated was collected by centrifugalseparation, and dried in vacuum. Further, the resulting polyrotaxane wasdissolved into DMSO, precipitated in water, collected and dried toobtain a purified polyrotaxane. A clathration amount of α-CD at thistime was 0.25.

Here, with regard to the clathration amount, the polyrotaxane wasdissolved into DMSO-d6, and NMR thereof was measured by ¹H-NMRSpectrometer (JNM-LA500, manufactured by JEOL Ltd.), and the clathrationamount was calculated by the following method.

Here, X, Y and X/(Y-X) indicate the following meanings.

X: an integrated value at 4-6 ppm for protons from a hydroxyl group ofcyclodextrin

Y: an integrated value at 3-4 ppm for protons from methylene chains ofcyclodextrin and PEG

X/(Y-X): A Proton Ratio of Cyclodextrin to PEG

First, the clathration amount was calculated by theoreticallycalculating in advance X/(Y-X) given at a maximum clathration amount of1, and comparing this calculated value with X/(Y-X) calculated from ananalytical value of an actual compound.

(1-3) Introduction of a Side Chain into a Polyrotaxane

Into 50 mL of 1 mol/L NaOH aqueous solution, 500 mg of the purifiedpolyrotaxane described above was dissolved, 3.83 g (66 mmol) ofpropylene oxide was added thereto, and under an argon atmosphere, theresulting mixture was stirred at room temperature for 12 hours.Subsequently, the polyrotaxane solution described above was neutralizedto be 7 to 8 in pH by using a 1 mol/L HCl aqueous solution, and theresulting material was dialyzed using a dialysis tube, and thenfreeze-dried to obtain a hydroxypropylated polyrotaxane.

In addition, a degree of modification to a OH group of the cyclicmolecule by a hydroxypropyl group was 0.5. A mixed liquid in which 5 gof hydroxypropylated polyrotaxane obtained was dissolved into 22.5 g ofε-caprolactone at 80° C. was prepared. This mixed liquid was stirred at110° C. for 1 hour while blowing dry nitrogen, and then 0.16 g of 50 wt% xylene solution of tin(II) 2-ethylhexanoate was added thereto, and theresulting mixture was stirred at 130° C. for 6 hours. Then, xylene wasadded thereto to obtain a xylene solution of a polycaprolactone-modifiedpolyrotaxane into which a side chain was introduced, in which anonvolatile concentration was about 35% by mass.

The xylene solution of the polycaprolactone-modified polyrotaxaneprepared as described above was added dropwise into hexane, and theresulting material was collected and dried to obtain a polyrotaxanemodified with a side chain having a primary hydroxyl group as apolymerizable functional group (polyrotaxane in which a molecular weightof the side chain of the polyrotaxane obtained was about 500 on anaverage, and according to measurement by GPC, a weight average molecularweight (Mw) of the polyrotaxane obtained was 400,000, and a hydroxylvalue was 1.35 mmol/g in a measured value.).

In addition, in Examples, the weight average molecular weight of thepolyrotaxane was measured using Gel Permeation Chromatography (GPC)under the following conditions:

Measuring instrument: Liquid Chromatography (manufactured by NihonWaters K. K.)

GPC column: Shodex GPC KF-805 (exclusion limit molecular weight:2,000,000) (manufactured by Showa Denko K. K.)

Flow rate: 1 mL/min

Column temperature: 40° C.

Sample concentration: 0.5% (w/v) (diluted with DMF)

Mobile phase solvent: DMF

Standard polystyrene equivalent

The hydroxyl value of the polyrotaxane was measured by a titrationmethod.

(1-4) Preparation of a Polyrotaxane (AI-1) Having a Tertiary HydroxylGroup in a Side Chain

To 5 g of this polyrotaxane, 15 g of xylene and 0.005 g ofdibutylhydroxytoluene (polymerization inhibitor) were added, and thenunder an argon atmosphere, 1.26 g of 2-methyl-2-(trimethylsiloxy)propylisocyanate was added dropwise thereto. In addition,2-methyl-2-(trimethylsiloxy)propyl isocyanate was added dropwise theretoso as to cause a reaction with a hydroxyl group of the polyrotaxane at aratio of 1/1. The resulting mixture was stirred at 40° C. for 16 hoursto obtain a xylene solution of a polyrotaxane in which a side chainhaving a hydroxyl group protected was introduced into an end ofpolycaprolactone.

This xylene solution of the polyrotaxane was added dropwise into hexane,the resulting material was collected, and then 20 g of THF was addedthereto, and under an argon atmosphere, a TBAF THF solution (10 mL, 1.0M) was added thereto, and the resulting mixture was stirred underheating reflux. After completion of the reaction, a saturated NH₄Claqueous solution was added thereto to separate a liquid, and an aqueouslayer was subjected to extraction with toluene, and a collected oillayer was dried over Na₂SO₄. Then, the solvent was removed under reducedpressure. Thus, a polyrotaxane (AI-1) being characterized in that a sidechain having a tertiary hydroxyl group was introduced into at least partof the cyclic molecule was able to be obtained. A molecular weight ofthe side chain of the polyrotaxane obtained was about 600 on an average,and according to measurement by GPC, a weight average molecular weight(Mw) of the polyrotaxane obtained was 460,000, and the hydroxyl group inthe side chain was 100% in the tertiary hydroxyl group.

AI-2: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

(1-5) Preparation of a Polyrotaxane (AI-2) Having a Tertiary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-2) having a tertiary hydroxyl group in a side chainwas obtained completely in the same manner as in the (AI-1) except thatPEG having a weight average molecular weight of 10,000 was used in placeof the PEG having the weight average molecular weight of 20,000 in(1-1).

Physical properties of this polyrotaxane (AI-2) were as described below:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 600 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 230,000

100% in the tertiary hydroxyl group as the hydroxyl group in the sidechain

AI-3: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

(1-6) Preparation of a Polyrotaxane (AI-3) Having a Tertiary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-3) having a tertiary hydroxyl group in a side chainwas obtained completely in the same manner as in the (AI-1) except thatan amount of ε-caprolactone in (1-3) was changed to 125 g.

Physical properties of this polyrotaxane (AI-3) were as described below:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 2,500 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 1,900,000

100% in the tertiary hydroxyl group as the hydroxyl group in the sidechain

AI-4: Polyrotaxane Having a Secondary Hydroxyl Group in a Side Chain

(1-7) Preparation of a Polyrotaxane (AI-4) Having a Secondary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-4) having a secondary hydroxyl group in a side chainwas obtained completely in the same manner as in the (AI-1) except that1.45 g of 2-(t-butyldimethylsiloxy)propyl isocyanate was used in placeof 2-methyl-2-(trimethylsiloxy)propyl isocyanate in (1-4).

Physical properties of this polyrotaxane (AI-4) were as described below:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 600 on an average Weight averagemolecular weight (Mw) of polyrotaxane (GPC): 460,000

100% in the secondary hydroxyl group as the hydroxyl group in the sidechain

AI-5: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

(1-8) Preparation of a Polyrotaxane (AI-5) Having a Tertiary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-5) having a tertiary hydroxyl group in a side chainwas obtained completely in the same manner as in the (AI-1) except thatPEG having a weight average molecular weight of 10,000 was used in placeof the PEG having the weight average molecular weight of 20,000 in(1-1), and 22.5 g of ε-caprolactam was used in place of ε-caprolactonein (1-3).

Physical properties of this polyrotaxane (AI-5) were as described below:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 600 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 230,000

100% in the tertiary hydroxyl group as the hydroxyl group in the sidechain

AI-6: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

(1-8) Preparation of a Polyrotaxane (AI-6) Having a Tertiary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-6) having a tertiary hydroxyl group in a side chainwas obtained completely in the same manner as in the (AI-1) except that22.5 g of γ-valerolactone was used in place of ε-caprolactone in (1-3).

Physical properties of this polyrotaxane (AI-6) were as described below:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 500 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 400,000

100% in the tertiary hydroxyl group as the hydroxyl group in the sidechain

AI-7: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

(1-9) Preparation of a Polyrotaxane (AI-7) Having a Tertiary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-7) having a tertiary hydroxyl group in a side chainwas obtained in the same manner as in the preparation method for the(AI-1) except that PEG having a weight average molecular weight of90,000 was used in place of the PEG having the weight average molecularweight of 20,000 in (1-1), and an amount of ε-caprolactone in (1-3) waschanged to 12.5 g.

Physical properties of this polyrotaxane (AI-7) were as described below:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 400 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 1,500,000

100% in the tertiary hydroxyl group as the hydroxyl group in the sidechain

AI-8: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

(1-10) Preparation of a Polyrotaxane (AI-8) Having a Tertiary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-8) having a tertiary hydroxyl group in a side chainwas obtained in the same manner as in the preparation method for the(AI-1) except that an amount of 2-methyl-2-(trimethylsiloxy)propylisocyanate was changed to 0.63 g in (1-4).

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 550 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 430,000

50% in the tertiary hydroxyl group and 50% in the primary hydroxyl groupas the hydroxyl group in the side chain

AI-9: Polyrotaxane Having a Tertiary Hydroxyl Group in a Side Chain

(1-11) Preparation of a Polyrotaxane (AI-9) Having a Tertiary HydroxylGroup in a Side Chain:

A polyrotaxane (AI-9) having a tertiary hydroxyl group in a side chainwas obtained in the same manner as in the preparation method inpreparation method for the (AI-1) except that an amount of2-methyl-2-(trimethylsiloxy)propyl isocyanate was changed to 1.01 g in(1-4).

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 600 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 450,000

80% in the tertiary hydroxyl group and 20% in the primary hydroxyl groupas the hydroxyl group in the side chain

The features of the (A) polyrotaxanes (AI-1) to (AI-9) prepared asdescribed above were summarized in Table 1.

TABLE 1 (A) Polyrotaxane Weight Molecular Clathration Degree of averageStraight- weight of amount of modification Molecular molecular chainstraight cyclic Side-chain of side weight of weight of molecule chainCyclic molecule molecule molecule chain Shape of side chain end sidechain polyrotaxane AI-1 PEG 20,000 α-Cyclodextrin 0.25 ε-Caprolactone0.5 Tertiary hydroxyl group 600 460,000 100% AI-2 PEG 10,000α-Cyclodextrin 0.25 ε-Caprolactone 0.5 Tertiary hydroxyl group 600230,000 100% AI-3 PEG 20,000 α-Cyclodextrin 0.25 ε-Caprolactone 0.5Tertiary hydroxyl group 2,500 1,900,000 100% AI-4 PEG 20,000α-Cyclodextrin 0.25 ε-Caprolactone 0.5 Secondary hydroxyl group 600460,000 100% AI-5 PEG 10,000 α-Cyclodextrin 0.25 ε-Caprolactam 0.5Tertiary hydroxyl group 600 230,000 100% AI-6 PEG 20,000 α-Cyclodextrin0.25 γ-Valerolactone 0.5 Tertiary hydroxyl group 500 400,000 100% AI-7PEG 90,000 α-Cyclodextrin 0.25 ε-Caprolactone 0.5 Tertiary hydroxylgroup 400 1,500,000 100% AI-8 PEG 20,000 α-Cyclodextrin 0.25ε-Caprolactone 0.5 Tertiary hydroxyl group/ 550 430,000 Primary hydroxylgroup 50%/50% AI-9 PEG 20,000 α-Cyclodextrin 0.25 ε-Caprolactone 0.5Tertiary hydroxyl group/ 600 450,000 Primary hydroxyl group 80%/20%

(A) Preparation of a polyrotaxane being characterized in that a sidechain having a hydroxyl group a pKa of which is 6 or more and less than14 is introduced into at least part of a cyclic molecule (polyrotaxaneaccording to Aspect II):

AII-1: Polyrotaxane Having a Hydroxyl Group a pKa of which is 10 in aSide Chain

A preparation method for a polyrotaxane (AII-1) will be described below.

The operation up to “(1-3) Introduction of a side chain into apolyrotaxane” described above was performed in the same manner as in thepreparation method for the polyrotaxane (AI-1).

A polyrotaxane modified with a side chain having a primary hydroxylgroup as a polymerizable functional group obtained in “(1-3)Introduction of a side chain to a polyrotaxane” being the preparationmethod for the polyrotaxane (AI-1) (polyrotaxane in which a molecularweight of the side chain of the polyrotaxane obtained was about 500 onan average, and according to measurement by GPC, a weight averagemolecular weight (Mw) of the polyrotaxane obtained was 400,000, and ahydroxyl value was 1.35 mmol/g in a measured value.) was a polyrotaxanemodified with a side chain having a primary hydroxyl group a pKa ofwhich is 15.5 (H-A in the formula (2): methanol).

(1-4) Preparation of a Polyrotaxane Having a Hydroxyl Group a pKa ofwhich is 10 in a Side Chain

To 5 g of this polyrotaxane, 15 g of xylene and 0.005 g ofdibutylhydroxytoluene (polymerization inhibitor) were added, and thenunder an argon atmosphere, 1.59 g of1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene was added dropwisethereto, in which 1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzenewas added dropwise thereto to be equimolar with the mole of the hydroxylgroup in the polyrotaxane. The resulting mixture was stirred at 40° C.for 16 hours, and overall consumption of the raw materials was confirmedto obtain a xylene solution of a polyrotaxane in which a side chainhaving a hydroxyl group protected was introduced into an end ofpolycaprolactone.

This xylene solution of the polyrotaxane was added dropwise into hexane,the resulting material was collected, and then 20 g of THF was addedthereto, and under an argon atmosphere, a tetra-n-butylammonium fluoride(TBAF) THF solution (10 mL, 1.0 M) was added thereto, and the resultingmixture was stirred under heating reflux. After completion of thereaction, a saturated NH₄C1 aqueous solution was added thereto toseparate a liquid, and an aqueous layer was subjected to extraction withtoluene, and a collected oil layer was dried over Na2SO4. Then, thesolvent was removed under reduced pressure, and a polyrotaxane in whicha side chain having a hydroxyl group a pKa of which is 10 in a sidechain was introduced into at least part of a cyclic molecule was able tobe obtained (H-A in the formula (2): phenol). In addition, the pKa isexpressed in terms of a value in water, and the pKa described in (a)“Handbook of Chemistry edited by the Chemical Society of Japan” (3^(rd)edition, published on June 25, 1984, published by Maruzen Co., Ltd.).With regard to the pKa not described in (a), a value of pKa can beobtained by carrying out measurement according to the method describedin (b) The Journal of Physical Chemistry, vol. 68, number 6, page 1560(1964). A molecular weight of the side chain of the polyrotaxaneobtained was about 650 on an average, and according to measurement byGPC, a weight average molecular weight of the polyrotaxane obtained was477,000. Moreover, with regard to the hydroxyl group at the end, fromoverall consumption of1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene, all the hydroxylgroups of the polyrotaxane obtained in (1-3) were substituted.

AII-2: Preparation of a Polyrotaxane Having a Hydroxyl Group a pKa ofwhich is 10 in a Side Chain

(1-5) Preparation of a Polyrotaxane (AII-2) Having a Hydroxyl Group apKa of which is 10 in a Side Chain:

A polyrotaxane (AII-2) having a hydroxyl group a pKa of which is 10 in aside chain was obtained completely in the same manner as in the (AII-1)except that PEG having a weight average molecular weight of 10,000 wasused in place of the PEG having the weight average molecular weight of20,000 in (1-1).

Physical properties of this polyrotaxane (AII-2) were as describedbelow:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 650 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 239,000

100% in the hydroxyl group the pKa of which is 10 in the side chain (H-Ain the formula (2): phenol)

AII-3: Preparation of a Polyrotaxane Having a Hydroxyl Group a pKa ofwhich is 10 in a Side Chain

(1-6) Preparation of a Polyrotaxane (AII-3) Having a Hydroxyl Group apKa of which is 10 in a Side Chain:

A polyrotaxane (AII-3) having a hydroxyl group a pKa of which is 10 in aside chain was prepared completely in the same manner as in the (AII-1)except that an amount of ε-caprolactone in (1-3) was changed to 125 g.

Physical properties of this polyrotaxane (AII-3) were as describedbelow:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 2,500 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 1,900,000

100% in the hydroxyl group the pKa of which is 10 in the side chain (H-Ain the formula (2): phenol)

AII-4: Polyrotaxane Having a Hydroxyl Group a pKa of which is 9.3 in aSide Chain

(1-7) Preparation of a Polyrotaxane (AII-4) Having a Hydroxyl Group apKa of which is 9.3 in a Side Chain:

A saturated solution of 140 mL of dichloromethane and 140 mL of NaHCO₃was added to 1.94 g of3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneamine atroom temperature, and then the resulting mixture was cooled to 0° C.while stirring the mixture, and then stirring was stopped. Then, theliquid was separated into two layers, and then 1.35 g of triphosgenedissolved in a dichloromethane solution (15 mL) was added to an organiclayer with a syringe, and the resulting mixture was immediately stirredagain for 30 minutes. Then, the mixture was separated into an aqueouslayer and an organic layer, the aqueous layer was subjected to liquidseparation and extraction with dichloromethane again, and then amoisture was removed from the organic layer with Na₂SO₄, and theresulting mixture was concentrated to be taken as3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneisocyanate. Then, to3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneisocyanate concentrated, under an argon atmosphere, 5 g of thepolyrotaxane synthesized in (1-3), 15 g of xylene and 0.005 g ofdibutylhydroxytoluene (polymerization inhibitor) were added, and thenunder the argon atmosphere, the resulting mixture was stirred at 40° C.for 16 hours. Completion of the reaction was confirmed by overallconsumption of3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneisocyanate to obtain a xylene solution of a polyrotaxane in which a sidechain having a hydroxyl group protected was introduced into an end ofthe polycaprolactone.

This xylene solution of the polyrotaxane was added dropwise into hexane,and the resulting material was collected, and then a mixed solution of18 g of THF and 2 g of Me0H was added thereto. Further, 0.07 g of 10%Pd/C was added thereto at room temperature, and then an atmosphere wasreplaced by hydrogen, the resulting mixture was stirred at 60° C. for1.5 hours, and a polyrotaxane being characterized in that a side chainhaving a hydroxyl group a pKa of which is 9.3 was introduced thereintowas able to be obtained (H-A in the formula (2): (CF₃)₂—CH₂—OH). Amolecular weight of the side chain of the polyrotaxane obtained wasabout 700 on an average, and according to measurement by GPC, a weightaverage molecular weight (Mw) of the polyrotaxane obtained was 470,000.Moreover, all the hydroxyl groups at the end were substituted becauseall of 1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene wereconsumed.

Physical properties of this polyrotaxane (AII-4) were as describedbelow:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 700 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 500,000

100% in the hydroxyl group the pKa of which is 9.3 in the side chain(H-A in the formula (2): (CF₃)₂—CH₂—OH)

AII-5: Preparation of a Polyrotaxane Having a Hydroxyl Group a pKa ofwhich is 12.5 in a Side Chain

(1-8) Preparation of a Polyrotaxane (A-5) Having a Hydroxyl Group a pKaof which is 12.5 in a Side Chain:

A polyrotaxane (A-5) having a hydroxyl group a pKa of which is 12.5 in aside chain was obtained in the same manner as in the preparation methodfor the (AII-4) except that 1.58 g of4,4,4-trifluoro-3-(phenylmethoxy)-1-butaneamine was applied in place of3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneamine in(1-7) (H-A in the formula (2): CF₃—CH₂—OH).

Physical properties of this polyrotaxane (AII-5) were as describedbelow:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 650 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 477,000

100% in the hydroxyl group the pKa of which is about 12.5 in the sidechain (H-A in the formula (2): CF₃—CH₂—OH)

AII-6: Polyrotaxane Having a Hydroxyl Group a pKa of which is 10 in aSide Chain

(1-9) Preparation of a Polyrotaxane Having a Hydroxyl Group a pKa ofwhich is 10 in a Side Chain:

A polyrotaxane (AII-6) having a hydroxyl group a pKa of which is 10 in aside chain was obtained in the same manner as in the preparation methodfor the (AII-1) except that PEG having a molecular weight of 90,000 wasused in place of the PEG having the weight average molecular weight of20,000 in (1-1), and an amount of ε-caprolactone in (1-3) was changed to10.5 g.

Physical properties of this polyrotaxane (AII-6) were as describedbelow:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 400 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 1,500,000

100% in the hydroxyl group the pKa of which is 10 in the side chain (H-Ain the formula (2): phenol)

AII-7: Polyrotaxane Having a Hydroxyl Group a pKa of which is 10 in aSide Chain

(1-10) Preparation of a Polyrotaxane (AII-7) Having a Hydroxyl Group apKa of which is 10 in a Side Chain:

A polyrotaxane (AII-7) having a hydroxyl group a pKa of which is 10 in aside chain was obtained in the same manner as in the preparation methodfor the (AII-1) except that an amount of1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene was changed to0.80 g in (1-4).

Physical properties of this polyrotaxane (AII-7) were as describedbelow:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 600 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 439,000

50% in the hydroxyl group the pKa of which is 10 in the side chain (H-Ain the formula (2): phenol) and 50% in the hydroxyl group the pKa ofwhich is 15.5 in the side chain (H-A in the formula (2): methanol)

AII-8: Polyrotaxane Having a Hydroxyl Group a pKa of which is 10 in aSide Chain

(1-11) Preparation of a Polyrotaxane (AII-8) Having a Hydroxyl Group apKa of which is 10 in a Side Chain:

A polyrotaxane (AII-8) having a hydroxyl group a pKa of which is 10 in aside chain was obtained in the same manner as in the preparation methodfor the (AII-1) except that an amount of1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene was changed to1.43 g in (1-4).

Physical properties of this polyrotaxane (AII-8) were as describedbelow:

Clathration amount of α-CD: 0.25

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 650 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 470,000

90% in the hydroxyl group the pKa of which is 10 in the side chain (H-Ain the formula (2): phenol) and 10% in the hydroxyl group the pKa ofwhich is 15.5 in the side chain (H-A in the formula (2): methanol)

Features of the (A) polyrotaxanes (AII-1) to (AII-8) prepared asdescribed above were summarized in Table 2.

TABLE 2 (A) Polyrotaxane Weight Molecular Clathration Degree of averageStraight- weight of amount of modification Molecular molecular chainstraight cyclic Side-chain of side weight of weight of molecule chainCyclic molecule molecule molecule chain Shape of side chain end sidechain polyrotaxane AII-1 PEG 20,000 α-Cyclodextrin 0.25 ε-Caprolactone0.5 pKa = 10 650 477,000 100% AII-2 PEG 10,000 α-Cyclodextrin 0.25ε-Caprolactone 0.5 pKa = 10 650 239,000 100% AII-3 PEG 20,000α-Cyclodextrin 0.25 ε-Caprolactone 0.5 pKa = 10 2,500 1,900,000 100%AII-4 PEG 20,000 α-Cyclodextrin 0.25 ε-Caprolactone 0.5 pKa = 9.3 700500,000 100% AII-5 PEG 20,000 α-Cyclodextrin 0.25 ε-Caprolactone 0.5 pKa= 12.5 650 477,000 100% AII-6 PEG 90,000 α-Cyclodextrin 0.25ε-Caprolactone 0.5 pKa = 10 400 1,500,000 100% AII-7 PEG 20,000α-Cyclodextrin 0.25 ε-Caprolactone 0.5 pKa = 10/pKa = 15.5 600 439,00050%/50% AII-8 PEG 20,000 α-Cyclodextrin 0.25 ε-Caprolactone 0.5 pKa =10/pKa = 15.5 650 470,000 90%/10%

(B) Compound Having Two or More Groups of at Least One Kind of GroupSelected from an Isocyanate Group and an Isothiocyanate Group in OneMolecule:

XDI: m-xylene diisocyanate

NBDI: (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene diisocyanate

HXDI: 1,3-bis(isocyanatomethyl)cyclohexane

(C) Iso(thio)Cyanate Reactive Group-Containing Compound

(C-1) Poly(thi)ol Compound Having Two or More Groups of at Least oneKind of Group Selected from a Hydroxyl Group and a Tthiol Group in OneMolecule

PL1: DURANOL, manufactured by Asahi Kasei Chemicals Co., Ltd.(polycarbonate diol, number average molecular weight: 500)

TMP: trimethylolpropane

PNT-40: pentaerythritol polyoxyethylene ether (tetrafunctional polyol,manufactured by Nippon Nyukazai Co., Ltd.)

Polythiol:

PEMP: pentaerythritol tetrakis(3-mercaptopropionate)

DPMP: dipentaerythritol hexakis(3-mercaptopropionate)

EGMP-4: tetraethylene glycol bis(3-mercaptopropionate)

PRX: polyrotaxane having a primary hydroxyl group in a side chain

A polyrotaxane having a primary hydroxyl group in a side chain obtainedin “(1-3) Introduction of a side chain into a polyrotaxane” in theprocess of producing AI-1 (H-A in the formula (2): methanol)

Degree of modification with side chain: 0.5

Molecular weight of side chain: about 500 on an average

Weight average molecular weight (Mw) of polyrotaxane (GPC): 400,000

100% in the primary hydroxyl group as the hydroxyl group in the sidechain (H-A in the formula (2): methanol)

(C-2) Mono(thi)ol Compound Having One Hydroxyl Group or One Thiol Groupin One Molecule:

PGME10: polyethylene glycol monooleyl ether (n≈10, Mw=668) 3-MBMA:3-methoxybutyl thioglycolate 1-DT: dodecanethiol

Photochromic compound (D): PC1:

(F) Polymerization curing accelerator:

Reaction catalyst for urethane or urea:

DBTD: dibutyltin dilaurate

(G) Internal mold release agent:

DBP: di-n-butyltin

PA2EE: phosphoric acid 2-ethylhexyl (mono- and di-mixture)

Other blends

Stabilizer:

HALS: bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (molecular weight:508)

Example I-1

A homogeneous liquid (optical composition) was prepared by mixing eachcomponent according to the following formulation. Each blending amountis shown in Table 3.

Formulation:

(A) Polyrotaxane: 8 parts by mass of AI-1

(B) Polyisocyanate compound: 47 parts by mass of NBDI

(C) Poly(thi)ol compound: 20 parts by mass of PL1, 16 parts by mass ofTMP,

-   -   Mono(thi)ol compound: 9 parts by mass of PGME10

(D) Photochromic compound: 0.04 part by mass of PC1

(H) Internal mold release agent: 0.3 part by mass of PA2EE (based on atotal amount of the mixture)

(Other blends): 0.1 part by mass of HALS

A photochromic cured body was obtained according to a kneading method byusing the optical composition. A polymerization method is describedbelow.

More specifically, the homogeneous liquid was sufficiently defoamed, andthen cast into two kinds of mold forms, including a glass mold designedto be 2 mm and 10 mm in a thickness of a cured body obtained, and acasting mold formed of a gasket composed of an ethylene-vinyl acetatecopolymer. Subsequently, while a temperature was gradually raised from30° C. to 100° C., the composition was cured in 15 hours. Aftercompletion of polymerization, a photochromic cured body was removed fromthe glass mold of the form to obtain the photochromic cured bodieshaving a thickness of 2 mm and a thickness of 10 mm. Photochromiccharacteristics, Rockwell hardness L scale (HL), moldability andcloudiness of the photochromic cured body (2 mm-thick) obtained wereevaluated. As a result, a maximum absorption wavelength was 577 nm,color optical density was 0.89, a color fading rate was 52 seconds,Rockwell hardness L scale (HL) was 77, moldability-1 was 1, andcloudiness-1 was 1. Moreover, moldability and cloudiness of thephotochromic cured body (10 mm-thick) were evaluated. As a result,moldability-2 was 1, and cloudiness-2 was 1. In addition, the maximumabsorption wavelength, the color optical density, the color fading rate,the Rockwell hardness L scale, the moldability-1 and the moldability-2,and the cloudiness-1 and the cloudiness-2 were evaluated according tothe methods described below.

[Evaluation Itemsx]

(1) Maximum absorption wavelength (λmax): A maximum absorptionwavelength after color development, which was determined usingSpectrophotometer (Instantaneous Multi Channel Photo Detector MCPD1000),manufactured by Otsuka Electronics Co., Ltd., after a photochromic curedbody (2 mm-thick) obtained was applied as a sample, and irradiated withlight having a beam intensity of 2.4 mW/cm² at 365 nm and 24 μW/cm² at245 nm on a surface of the cured body at 20° C.±1° C. for 120 secondsthrough Aero Mass Filter (manufactured by Corning Corporation) by usingXenon Lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics K.K. to develop color. The maximum absorption wavelength relates to acolor tone during color development.

(2) Color optical density {ε(120)−ε(0)}: A difference between, at themaximum absorption wavelength, an absorbance (ε(120)) after irradiationwith light for 120 seconds and an absorbance (ε(0)) before irradiationwith light. As this value is higher, the photochromism may be reasonablyreferred to as being superb. Moreover, when the color was developedoutdoors, a coloring tone was visually evaluated.

(3) Color fading rate [t1/2(sec)]: A time required for reduction to onehalf of {ε(120)−ε(0)} in the absorbance at the maximum absorptionwavelength of the sample upon irradiating the sample with light for 120seconds and then stopping the irradiation with light. As this time isshorter, the photochromism may be reasonably referred to as beingsuperb.

(4) Rockwell hardness L scale (HL): Rockwell harness L scale of thephotochromic cured body (2 mm-thick) was measured using Akashi RockwellHardness Tester (Model: AR-10) after the cured body (2 mm-thick) waskept at 25° C. for one day in a room.

(5) Moldability-1:

Optical strain of the photochromic cured body (2 mm-thick) was visuallyobserved. Evaluation criteria are as described below.

1: Free from optical strain

2: Optical strain partially observable in a half part or less of a lens

3: Optical strain observable wholly in a lens

(6) Cloudiness-1:

Cloudiness of the photochromic cured body (2 mm-thick) was visuallyevaluated. Evaluation criteria are as described below.

1: Level having no problem as a product, and free from cloudiness oralmost invisible

2: Level having no problem as a product, but somewhat cloudy

3: Level having no problem as a product, but stronger in cloudiness thanthe level 2

4: Cloudy, and unusable as a product

(7) Moldability-2:

Optical strain of the cured body (10 mm-thick) was evaluated using ahigh-pressure mercury lamp. More specifically, a surface of the curedbody (10 mm-thick) was irradiated with light from the high-pressuremercury lamp, and moldability was evaluated by visually observing aprojection thereof. Evaluation criteria are as described below.

1: Free from optical strain

2: Optical strain partially observable in a half part or less of a lens

3: Optical strain observable in a half part or more of a lens

4: Optical strain observable wholly in a lens

(8) Cloudiness-2:

Cloudiness of the cured body (10 mm-thick) was evaluated using ahigh-pressure mercury lamp. More specifically, a side surface of thecured body (10 mm-thick) was irradiated with light from thehigh-pressure mercury lamp, and a degree of cloudiness was evaluated byvisually observing the cured body (10 mm-thick) from the surface.Evaluation criteria are as described below.

1: Free from cloudiness or almost invisible

2: Level having no problem as a product, but somewhat cloudy

3: Level having no problem as a product, but stronger in cloudiness thanthe level 2

4: Cloudy, and unusable as a product

Example I-2 to I-11, Comparative Examples I-1 to I-3

A photochromic cured body was prepared in the same manner as in ExampleI-1 except that a photochromic optical composition having a formulationshown in Table 3 was used, and the resulting material was evaluated. Theresults were shown in Table 4. Moreover, the photochromic compound (D)component was not added thereto in Example I-11 and Comparative Example1-3, and therefore the photochromic characteristics were not measured.Moreover, moldability-1 and cloudiness-1 were evaluated with referenceto Patent literature 8.

TABLE 3 (A) Component (B) Component (parts by (parts by (C) Component(D) (F) (G) Other No. mass) mass) (parts by mass) Component ComponentComponent blends Example I-1 AI-1 (8) NBDI (47) PL1 (20)/TMP (16)/PGME10PC1 (0.04) — PA2EE (0.3) HALS (9) (0.1) Example I-2 AI-2 (10) NBDI (36)PNT-40 (19)/PL1 (24)/ PC1 (0.04) — PA2EE (0.3) — PGME10 (11) Example I-3AI-5 (12) NBDI (52) PL1 (16)/TMP (20) PC1 (0.04) — PA2EE (0.3) HALS(0.1) Example I-4 AI-3 (16) XDI (37) PEMP (47) PC1 (0.04) DBTD DBP (0.3)— (0.1) Example I-5 AI-4 (5) XDI (40) DPMP (50)/3-MBMA (5) PC1 (0.04)DBTD DBP (0.3) — (0.1) Example I-6 AI-6 (2) XDI (39) DPMP (48)/1-DT (11)PC1 (0.04) DBTD DBP (0.3) HALS (0.1) (0.1) Example I-7 AI-7 (5) XDI (40)PEMP (46)/EGMP-4 (9) PC1 (0.04) DBTD DBP (0.3) — (0.1) Example I-8 AI-6(5) XDI (39) DPMP (46)/EGMP-4 (5)/3- PC1 (0.04) DBTD DBP (0.3) HALS MBMA(5) (0.1) (0.1) Example I-9 AI-8 (9) XDI (39) PEMP (43)/1-DT (9) PC1(0.04) DBTD — — (0.1) Example I- AI-9 (7) NBDI (55) PL1 (17)/TMP (21)PC1 (0.04) — PA2EE (0.3) — 10 Example I- AI-1 (6) XDI (40) DPMP (54) —DBTD DBP (0.3) — 11 (0.1) Comparative — NBDI (47) PL1 (20)/TMP(16)/PGME10 PC1 (0.04) — PA2EE (0.3) — Example I-1 (9)/PRX (8)Comparative — XDI (39) DPMP (46)/EGMP-4 (5)/3- PC1 (0.04) DBTD DBP (0.3)HALS Example I-2 MBMA (5)/PRX (5) (0.1) (0.1) Comparative — XDI (36)DPMP (50)/PRX (14) — DBTD DBP (0.3) HALS Example I-3 (0.1) (0.1)

TABLE 4 Maximum absorption Color wavelength Color optical fading rateNo. (λmax) density (second) HL Moldability-1 Cloudiness-1 Moldability-2Cloudiness-2 Example I-1 577 0.89 52 77 1 1 1 1 Example I-2 578 0.92 4877 1 1 1 1 Example I-3 579 0.78 55 95 1 1 2 1 Example I-4 585 0.64 53 991 1 2 2 Example I-5 584 0.79 51 76 1 1 1 1 Example I-6 584 0.57 55 88 11 1 1 Example I-7 590 0.58 72 82 1 1 2 1 Example I-8 585 0.88 50 75 1 11 1 Example I-9 584 0.60 52 84 1 1 1 2 Example I-10 579 0.74 56 96 1 1 21 Example I-11 — — — 110 1 1 1 1 Comparative 576 0.90 48 75 1 1 4 1Example I-1 Comparative 584 0.88 48 73 1 1 3 3 Example I-2 Comparative —— — 85 1 2 3 4 Example I-3

Example II-1

A homogeneous liquid (optical composition) was prepared by mixing eachcomponent according to the following formulation. Each blending amountis shown in Table 5.

Formulation:

(A) Polyrotaxane: 8 parts by mass of AII-1

(B) Polyisocyanate compound: 47 parts by mass of NBDI

(C) Poly(thi)ol compound: 22 parts by mass of PL1, 16 parts by mass ofTMP,

-   -   Mono(thi)ol compound: 7 parts by mass of PGME10

(D) Photochromic compound: 0.04 part by mass of PC1

(H) Internal mold release agent: 0.3 part by mass of PA2EE

(Other blends): 0.1 part by mass of HALS

A photochromic cured body was obtained according to a kneading method byusing the optical composition. A polymerization method will be describedbelow.

More specifically, the homogeneous liquid was sufficiently defoamed, andthen cast into two kinds of mold forms, including a glass mold designedto be 2 mm and 10 mm in a thickness of a cured body obtained, and acasting mold formed of a gasket composed of an ethylene-vinyl acetatecopolymer. Next, while a temperature was gradually raised from 30° C. to100° C., the composition was cured in 15 hours. After completion ofpolymerization, a photochromic cured body was removed from the glassmold of the form to obtain the photochromic cured bodies having athickness of 2 mm and a thickness of 10 mm. Photochromiccharacteristics, Rockwell hardness L scale (HL), moldability andcloudiness of the photochromic cured body (2 mm-thick) obtained wereevaluated. As a result, a maximum absorption wavelength was 579 nm,color optical density was 0.90, a color fading rate was 54 seconds,Rockwell hardness L scale (HL) was 80, moldability-1 was 1 andcloudiness-1 was 1. Moreover, moldability and cloudiness of thephotochromic cured body (10 mm-thick) were evaluated. As a result,moldability-was 1 and cloudiness-2 was 1. In addition, the maximumabsorption wavelength, the color optical density, the color fading rate,the Rockwell hardness L scale, the moldability-1 and the moldability-2,and the cloudiness-1 and the cloudiness-2 were evaluated according tothe methods described above.

Examples II-2 to II-8, Comparative Examples II-1 to II-3

A photochromic cured body was prepared in the same manner as in ExampleII-1 except that a photochromic optical composition having a formulationshown in Table 5 was used, and the resulting material was evaluated. Theresults were shown in Table 6. Moreover, the photochromic compound (D)component was not added thereto in Example 11-7 and Comparative Example11-3, and therefore the photochromic characteristics were not measured.Moreover, moldability-1 and cloudiness-1 were evaluated with referenceto Patent literature 8.

In addition, experiments in Comparative Examples I-1 to 1-3 are the sameexperiments in Comparative Examples II-1 to 11-3, respectively.

TABLE 5 (A) Component (B) Component (C) Component (D) (F) (G) Other No.(parts by mass) (parts by mass) (parts by mass) Component ComponentComponent blends Example II-1 AII-1 (8) NBDI (47) PL1 (22)/TMP (16)/PGME10 (7) PC1 (0.04) — PA2EE (0.3) HALS (0.1) Example II-2 AII-2 (5) NBDI(38) PNT-40 (20)/PL1 (25)/PGME10 PC1 (0.04) — PA2EE (0.3) — (12) ExampleII-3 AII-3 (8) XDI (40) PEMP (48)/3-MBMA (4) PC1 (0.04) DBTD DBP (0.3)HALS (0.1) (0.1) Example II-4 AII-4 (5) XDI (40) DPMP (45)/PEMP (10) PC1(0.04) DBTD DBP (0.3) — (0.1) Example II-5 AII-5 (12) HXDI (49) PL1(20)/TMP (19) PC1 (0.04) — PA2EE (0.3) HALS (0.1) Example II-6 AII-6 (8)XDI (39) PEMP (48)/EGMP-4 (6) PC1 (0.04) DBTD DBP (0.3) HALS (0.1) (0.1)Example II-7 AII-7 (5) XDI (42) PEMP (53) — DBTD DBP (0.3) — (0.1)Example II-8 AII-8 (4) XDI (40) DPMP (23)/EGMP-4 (7)/PEMP PC1 (0.04)DBTD DBP (0.3) HALS (24)/3-MBMA (2) (0.1) (0.1) Comparative — NBDI (47)PL1 (20)/TMP (16)/PGME10 (9)/ PC1 (0.04) — PA2EE (0.3) — Example II-1PRX (8) Comparative — XDI (39) DPMP (46)/EGMP-4 (5)/ PC1 (0.04) DBTD DBP(0.3) HALS Example II-2 3-MBMA (5)/PRX (5) (0.1) (0.1) Comparative — XDI(36) DPMP (50)/PRX (14) — DBTD DBP (0.3) HALS Example II-3 (0.1) (0.1)

TABLE 6 Maximum absorption wavelength Color optical Color fading rateNo. (λmax) density (second) HL Moldability-1 Cloudiness-1 Moldability-2Cloudiness-2 Example II-1 579 0.90 54 80 1 1 1 1 Example II-2 580 0.9149 79 1 1 1 1 Example II-3 589 0.84 55 97 1 1 2 2 Example II-4 585 0.7060 93 1 1 1 1 Example II-5 578 0.71 54 100 1 1 2 1 Example II-6 584 0.5852 85 1 1 1 2 Example II-7 — — — 105 1 1 1 2 Example II-8 588 0.88 50 751 1 1 1 Comparative 576 0.90 48 75 1 1 4 1 Example II-1 Comparative 5840.88 48 73 1 1 3 3 Example II-2 Comparative — — — 85 1 2 3 4 ExampleII-3

Example I-12

A homogeneous liquid (optical composition) was prepared by mixing eachcomponent according to the following formulation. Each blending amountis shown in Table 7.

Formulation:

(A) Polyrotaxane: 12 parts by mass of AI-1

(B) Polyisocyanate compound: 37 parts by mass of XDI

(C) Poly(thi)ol compound: 38 parts by mass of DPMP,

-   -   Mono(thi)ol compound: 13 parts by mass of 1-DT

(D) Photochromic compound: 0.04 part by mass of PC1

(F) Polymerization curing accelerator: 0.001 part by mass of DBTD:dibutyltin dilaurate (based on a total amount of the mixture)

(Other blends): 0.1 part by mass of HALS

A photochromic laminate was obtained according to a coating method byusing the optical composition. A polymerization method is describedbelow.

As an optical base material, a thiourethane-based plastic lens having acenter thickness of about 2 mm, a spherical power of −6.00 D, and arefractive index of 1.60 was arranged. In addition, with regard to thisthiourethane-based plastic lens, alkali etching was applied thereto inadvance at 50° C. for 5 minutes by using a 10% sodium hydroxide aqueoussolution, and then the resulting material was sufficiently washed withdistilled water.

A photochromic coating composition was added dropwise onto a surface ofthe plastic lens rotated at 2,000 rpm by using Spin Coater (1H-DX2,manufactured by MIKASA, Co., Ltd.). Then, a photochromic laminate wasobtained by heating the resulting material at 120° C. for 1 hour tocause polymerization curing. A film thickness of a photochromic layerwas about 30 μm.

In the photochromic laminate obtained, a maximum absorption wavelengthwas 586 nm, color optical density was 0.93, a color fading rate was 50seconds, Vickers hardness was 7, moldability-1 was 1 and cloudiness-1was 1. Moreover, moldability and cloudiness of the photochromic curedbody (10 mm-thick) were evaluated. As a result, moldability-2 was 1, andcloudiness-2 was 1. In addition, the maximum absorption wavelength, thecolor optical density, the color fading rate, the moldability-1 and themoldability-2, and the cloudiness-1 and the cloudiness-2 were evaluatedby the same methods as the methods in Example 1 or the like, and theVickers hardness was evaluated by the method described below. Thesemeasured values were shown in Table 8.

(9) Vickers hardness: Vickers hardness of the photochromic layerobtained was measured using Micro Vickers Hardness Testing MachinePMT-X7A (manufactured by Matsuzawa Co., Ltd.). The hardness wasevaluated by using a rectangular pyramid-type diamond indenter as anindenter and under conditions of a load of 10 gf and an indenter'sretention time of 30 seconds. Measurements four times in total werecarried out, a first value having a large measurement error wasexcluded, and the measurement results were shown in terms of a meanvalue of measurements three times.

Example II-9

A photochromic cured body was prepared in the same manner as in <Example1-12>except that a photochromic optical composition having a formulationshown in Table 7 was used, and was evaluated. The results were shown inTable 8.

TABLE 7 (A) Component (B) Component (C) Component Other No. (parts bymass) (parts by mass) (parts by mass) (D) Component (F) Component blendsExample I-12 AI-1 (12) XDI (37) DPMP (38)/1-DT (13) PC1 (0.04) DBTD HALS(0.001) (0.1) Example II-9 AII-1 (9) XDI (46) PEMP (35)/PGME10 (10) PC1(0.04) DBTD HALS (0.001) (0.1)

TABLE 8 Maximum absorption Color Color wavelength optical fading rateVickers No. (λmax) density (second) Moldability-1 Cloudiness-1Moldability-2 Cloudiness-2 hardness Example I-12 586 0.93 46 1 1 1 1 7Example II-9 593 0.85 49 1 1 1 1 9

As is evident from the Examples and the Comparative Examples describedabove, the cured body obtained by polymerizing the optical compositionaccording to the present invention has excellent moldability andmechanical strength, and further reduced cloudiness. Moreover, when thephotochromic compound is added thereto, the cured body is excellent inthe photochromic characteristics in addition to the physical propertiesdescribed above.

In contrast, in Comparative Examples I-1 and 1-2, while the photochromiccharacteristics, the moldability-1, the cloudiness-1 and the like weresatisfactory, the evaluation results of the moldability-2 and thecloudiness-2, which were severer, were insufficient. Moreover, also inComparative Example 3, the evaluation results of the moldability-2 andthe cloudiness-2 were insufficient.

Moreover, the optical composition according to the present invention canalso be applied to the coating method.

REFERENCE SIGNS LIST

1: Polyrotaxane

2: Axle molecule

3: Cyclic molecule

4: Bulky end group

5: Side chain having a secondary or tertiary hydroxyl group

1. An optical composition, comprising a polyrotaxane, wherein thepolyrotaxane comprises a composite molecular structure formed of an axlemolecule and a plurality of cyclic molecules clathrating the axlemolecule, wherein the polyrotaxane satisfies at least one ofrequirements (X) and (Y): requirement (X): a side chain having asecondary or tertiary hydroxyl group is introduced into at least part ofthe cyclic molecule of the polyrotaxane; and requirement (Y): a sidechain having a group represented by the following formula (1):-A   (1) (wherein, A is an organic group having 1 to 10 carbon atoms andcontains at least one hydroxyl group) is introduced into at least partof the cyclic molecule of the polyrotaxane; and a pKa of a hydroxylgroup of a compound represented by the following formula (2):H-A   (2) is 6 or more and less than
 14. 2. The optical compositionaccording to claim 1, further comprising a compound (B) having two ormore groups of at least one kind of group selected from an isocyanategroup and an isothiocyanate group in one molecule.
 3. The opticalcomposition according to claim 1, further comprising an iso(thio)cyanatereactive group-containing compound (C).
 4. The optical compositionaccording to claim 2, further comprising an iso(thio)cyanate reactivegroup-containing compound (C) .
 5. The optical composition according toclaim 1, further comprising a photochromic compound (D).
 6. The opticalcomposition according to claim 2, further comprising a photochromiccompound (D).
 7. The optical composition according to claim 3, furthercomprising a photochromic compound (D).
 8. The optical compositionaccording to claim 4, further comprising a photochromic compound (D). 9.The optical composition according to claim 1, wherein the polyrotaxanesatisfies the requirement (X).
 10. The optical composition according toclaim 9, wherein a proportion of a primary hydroxyl group is 50% orless, when the total mole number of primary, secondary and tertiaryhydroxyl groups of the side chain is taken as 100%.
 11. The opticalcomposition according to claim 9, wherein the side chain having thesecondary or tertiary hydroxyl group comprises a structure representedby the following formula (1):

[wherein, Q is formed of at least one kind selected from structuresrepresented by the following formulas (Q-1), (Q-2) and (Q⁻3):

(wherein, G is a straight-chain alkylene group or alkenylene grouphaving 1 to 8 carbon atoms; a branched-chain alkylene group oralkenylene group having 3 to 20 carbon atoms; an alkylene group oralkenylene group formed by replacement of a part of the alkylene groupor alkenylene group by a —O— bond, a —NH— bond, a —SO— bond or a —SiO—bond; or an alkylene group formed by replacement of a part of hydrogenof the alkylene group by at least one kind selected from the groupconsisting of a hydroxyl group, a carboxyl group, an acyl group, aphenyl group, a halogen atom and an olefin group, and when a pluralityof G exist, each G may be a same group or a different group, and n₁, n₂and n₃ are each independently an integer from 1 to 200), and when Q isformed of two or more kinds selected from the formulas (Q-1), (Q-2) and(Q-3), G constituting (Q-1) to (Q-3) may be a same group or a differentgroup, a total of n₁, n₂ and n₃ is an integer from 1 to 200, R¹ and R²are each independently a group selected from hydrogen, a straight-chainalkyl group having 1 to 6 carbon atoms and a branched-chain alkyl grouphaving 1 to 6 carbon atoms, excluding a group in which R¹ and R² aresimultaneously hydrogen].
 12. The polyrotaxane according to claim 9,wherein the side chain having the secondary or tertiary hydroxyl groupcomprises a structure represented by the following formula (1′):

[wherein, Q is formed of at least one kind selected from structuresrepresented by the following formulas (Q-1), (Q-2) and (Q⁻3):

(wherein, G is a straight-chain alkylene group or alkenylene grouphaving 1 to 8 carbon atoms; a branched-chain alkylene group oralkenylene group having 3 to 20 carbon atoms; an alkylene group oralkenylene group formed by replacement a part of the alkylene group oralkenylene group by a —O— bond, a —NH— bond, a —SO— bond or a —SiO—bond; or an alkylene group formed by replacement of a part of hydrogenof the alkylene group by at least one kind selected from the groupconsisting of a hydroxyl group, a carboxyl group, an acyl group, aphenyl group, a halogen atom and an olefin group, and when a pluralityof G exist, each G may be a same group or a different group, and ni, n2,n3 are each independently an integer from 1 to 200), and when Q isformed of two or more kinds selected from the formulas (Q-1), (Q-2) and(Q-3), G constituting (Q-1) to (Q-3) may be a same group or a differentgroup, a total of n₁, n₂ and n₃ is an integer from 1 to 200, X is analkylene group or alkenylene group having 2 to 20 carbons, or analkylene group or alkenylene group formed by replacement of a part ofthe alkylene group or alkenylene group by a —O— bond or a —NH— bond; R³and R⁴ are each independently selected from hydrogen, a straight-chainalkyl group having 1 to 6 carbon atoms or a branched-chain alkyl grouphaving 1 to 6 carbon atoms, excluding a group in which R³ and R⁴ aresimultaneously hydrogen; and R⁵ is carbon or sulfur].
 13. The opticalcomposition according to claim 1, wherein the polyrotaxane satisfies therequirement (Y).
 14. The optical composition according to claim 13,wherein a proportion of a hydroxyl group having a pKa of less than 6 or14 or more is 50% or less, when the total mole number of the hydroxylgroups of the side chain is taken as 100%.
 15. The optical compositionaccording to claim 13, wherein a side chain represented by the followingformula (3) is introduced into at least part of the cyclic molecule:-Q-A   (3) [wherein, Q is formed of at least one kind selected fromstructures represented by the following formulas (Q-1), (Q-2) and (Q⁻3):

(wherein, G is a straight-chain alkylene group or alkenylene grouphaving 1 to 8 carbon atoms; a branched-chain alkylene group oralkenylene group having 3 to 20 carbon atoms; an alkylene group oralkenylene group formed by replacement of a part of the alkylene groupor alkenylene group by a —O— bond, a —NH— bond, a —SO— bond or a —SiO—bond, or an alkylene group formed by replacement of a part of hydrogenof the alkylene group by at least one kind selected from the groupconsisting of a carboxyl group, an acyl group, a phenyl group, a halogenatom and an olefin group, and when a plurality of G exist, each G may bea same group or a different group, and n₁, n₂ and n₃ are eachindependently an integer from 1 to 200), and when Q is formed of two ormore kinds selected from the formulas (Q-1), (Q-2) and (Q-3), Gconstituting (Q-1) to (Q-3) may be a same group or a different group, atotal of n₁, n₂ and n₃ is an integer from 1 to 200, and A is an organicgroup having 1 to 10 carbon atoms, and contains at least one hydroxylgroup].
 16. The optical composition according to claim 13, wherein aside chain represented by the following formula (3′) is introduced intoat least part of the cyclic molecule:

[wherein, Q is formed of at least one kind selected from structuresrepresented by the following formulas (Q-1), (Q-2) and (Q⁻3):

(wherein, G is a straight-chain alkylene group or alkenylene grouphaving 1 to 8 carbon atoms; a branched-chain alkylene group oralkenylene group having 3 to 20 carbon atoms; an alkylene group oralkenylene group formed by replacement of a part of the alkylene groupor alkenylene group by a —O— bond, a —NH— bond, a —SO— bond or a —SiO—bond; or an alkylene group formed by replacement of a part of hydrogenof the alkylene group by at least one kind selected from the groupconsisting of a carboxyl group, an acyl group, a phenyl group, a halogenatom and an olefin group, and when a plurality of G exist, each G may bea same group or a different group, and n₁, n₂ and n₃ are eachindependently an integer from 1 to 200), and when Q is formed of two ormore kinds selected from the formulas (Q-1), (Q-2) and (Q-3), Gconstituting (Q-1) to (Q-3) may be a same group or a different group, atotal of n₁, n₂ and n3 is an integer from 1 to 200, and R⁶ is carbon orsulfur, X is an alkylene group or alkenylene group having 2 to 20carbons; or an alkylene group or alkenylene group formed by replacementof a part of the alkylene group or alkenylene group by a —O— bond or a—NH— bond, and A is an organic group having 1 to 10 carbon atoms andcontains at least one hydroxyl group].
 17. The optical compositionaccording to claim 1, wherein a ring contained in the cyclic molecule ofthe polyrotaxane is a cyclodextrin ring.
 18. The optical compositionaccording to claim 1, wherein the axle molecule threading through aninside of the ring of the cyclic molecule has a chain structure havingbulky groups at both ends, a chain portion is formed of polyethyleneglycol, and the bulky groups at both ends each is an adamantyl group.